JPS58151490A - Production of colored metallic plate electroplated with zinc - Google Patents

Abstract

PURPOSE:To obtain a metallic plate electroplated with zinc having dense and beautiful colored layers of dark color without application of heat treatment, by subjecting a metallic plate to composite zinc electroplating then to an anodic electrolyzing treatment in the same bath. CONSTITUTION:A metallic plate is subjected to zinc electroplating in an acidic zinc electroplating bath consisting essentially of Zn added with >=1 kind among water-soluble compds. of Co, Ni, Mo, at 3-50g/l Co, Ni and 0.01-3g/l Mo in terms of metal. In succession, the steel plate is subjected to an anodic electrolyzing treatment of 5-500 coulomb/dm<2> quantity of electricity with the plating plate as anode in the same plating bath. The plated metallic plate is thereafter dipped in an aq. soln. contg. silicic acid, silicate, chromic acid, chromate, etc. according to need, and is dried, whereby 10-400mg/m<2> (expressed in terms of Si) is coated thereon. The zinc electroplated metallic plate having the surfaces colored densely to bluish black - black colors is obtained by the above- mentioned method.

Description

【発明の詳細な説明】 本発明は着色電気亜鉛めっき金属板の製造法に関し、よ
り詳しくは金属板を、　Ｚｎの他にＣｏ、Ｎｉ或いはＭ
ｏ　ｏ＞　１種以上を含む浴中で複合磁気亜鉛めっきし
た後、同一浴中で陽極電解処理（第１処理）する事によ
り、表面な青黒色乃至黒色に着色せしめた着色電気亜鉛
めっき金属板を得る方法に関する。また、更に別浴で陰
極電解する方法にも関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a colored electrogalvanized metal sheet, and more specifically, the present invention relates to a method for producing a colored electrogalvanized metal sheet, and more specifically, the present invention relates to a method for manufacturing a colored electrogalvanized metal sheet, and more specifically, a method for producing a colored electrogalvanized metal sheet.
o o> A colored electrogalvanized metal plate whose surface is colored blue-black to black by performing composite magnetic galvanizing in a bath containing one or more types of galvanized metal, followed by anodic electrolytic treatment (first treatment) in the same bath. Regarding how to get . The present invention also relates to a method of cathodic electrolysis in a separate bath.

従来、装飾性や光吸収性、吸熱性、乃至は光の反射防止
性向上の見地より亜鉛表面の暗色線色法が各種試みられ
て米だ。これらの線色法は例えば（１）黒色塗料を塗布
する方法、Ｑ）塩素酸塩浸漬法、（３）モリブデン酸塩
浸漬法、（４）無水クロム酸浸漬法、（団硫化物浸漬法
、（６）硫酸鋼浸漬法その他がある。In the past, various attempts have been made to color the zinc surface with dark lines in order to improve its decorative properties, light absorption, heat absorption, and anti-reflection properties. These line coloring methods include, for example, (1) black paint application method, Q) chlorate dipping method, (3) molybdate dipping method, (4) chromic anhydride dipping method, (group sulfide dipping method, (6) There are other methods such as sulfuric acid steel dipping method.

しかし、上記（１）の方法はコストが尚く、安価な方法
では塗膜の密有性が良くないし、（り乃至（６）の方法
では処理浴の管理が面倒であり、廃液処理上の問題が生
じると共に、短時間処理で安定した暗色皮膜を得ること
が困難であった。However, the method (1) above is expensive, and cheaper methods do not provide good paint film tightness, and methods (6) to (6) require troublesome management of the treatment bath, making it difficult to treat waste liquid. Problems arose, and it was difficult to obtain a stable dark-colored film in a short period of time.

そこで本出願人は、基本的には先ず亜鉛めっき自体をコ
バルトおよび／またはニッケルとの合金めっきとし、上
記電気めっき製品を加熱することにより、極めて簡単に
めつき麺表面を暗色着色せしめ得ること、および更に耐
食性向上乃至外観特性の向上のために上記めっき液Ｊ：
有機添加剤を添加したり、めっき後表面に珪酸系後処理
を施したり、合成樹脂塗料を施すことにより、所望の着
色電気亜鉛めっき製品を製造し得ることを内容とする発
明を提案した（特開昭５５−９１９９３）。Therefore, the applicant has proposed that the surface of the plated noodles can be colored very easily by first alloying the zinc plating itself with cobalt and/or nickel and then heating the electroplated product. In order to further improve corrosion resistance and appearance characteristics, the above plating solution J:
We proposed an invention that enables the production of desired colored electrogalvanized products by adding organic additives, performing silicic acid post-treatment on the surface after plating, or applying a synthetic resin paint (special invention). (1993-91993).

しかるになお加熱法では省エネルギーの見地より問題が
残り、かつ着色程度のコントロールか困難であって必ず
しも均一な着色が得られず、また生産性や処理後の耐食
性がやや劣る等の間組点が生じる事が実施の結果判って
釆だ。However, the heating method still has problems from the standpoint of energy saving, and it is difficult to control the degree of coloring, so uniform coloring cannot always be obtained, and the productivity and corrosion resistance after treatment are slightly inferior, resulting in the occurrence of interpolation points. However, the results of implementation will be clear.

そこで更に本発明者はより後れた番色汰を思出する必要
に迫られ、種々実験、考察の結果、主としてめっき後に
一極電解処理（第ｌ処理）１°ることにより、Ｌ記間紬
点を解決し得ることを見出した。Therefore, the inventor of the present invention was forced to remember the later Banshita, and as a result of various experiments and considerations, mainly by performing 1 degree of unipolar electrolytic treatment (1st treatment) after plating, it was possible to We have discovered that we can solve the Tsumugi problem.

けだし、前記提案のとおり、ｃｏ、Ｎｉを含む合金亜鉛
めつき麺表面は加熱、すなわち酸化によって暗色着色す
る事実が知られており、この酸化現象を陽極電解処理に
よって浴中で惹起する事も可能と考えられたゆ１らであ
る。However, as proposed above, it is known that the surface of alloy galvanized noodles containing Co and Ni becomes dark colored by heating, that is, by oxidation, and it is also possible to induce this oxidation phenomenon in a bath by anodic electrolysis treatment. Yu1 et al.

すなわち、複合電気亜鉛めっきした金属板表面を陽極と
して浴中で電解処理（第１処ｍ）Ｔると、陽極表面にお
いて発生期の酸素０が発生し、めっき層が軽く再溶解さ
れると同時に酸化されるので、気中加熱と同様な酸化現
象が生じ、Ｃｏ、ＮｉもしくはＭＯの優先酸化が起って
着色するものと４えられ、しかも加熱の場合と異なって
ＭＯの酸化物粒子の発生を見ることもなく、ｍ密な着色
層が得られる事が実験の結果明らかになったのである。In other words, when the surface of a composite electrogalvanized metal plate is electrolytically treated (first step) in a bath using the surface as an anode, nascent oxygen is generated on the surface of the anode, and the plating layer is slightly redissolved. Because of the oxidation, an oxidation phenomenon similar to that of heating in air occurs, and it is thought that preferential oxidation of Co, Ni, or MO occurs, resulting in coloring4.Moreover, unlike in the case of heating, oxide particles of MO are generated. As a result of experiments, it became clear that an m-dense colored layer could be obtained without the need to see.

本発明の目的は加熱処理によらずに緻密美簾な着色層が
得られる有色電気亜鉛めっき金属板の製造法を提供する
φである。An object of the present invention is to provide a method for producing a colored electrogalvanized metal sheet that can provide a dense and beautiful colored layer without heat treatment.

本発明の他の目的は、処理時間が極めて短かく、亜鉛め
っき金属板の製造法を提供するにある。Another object of the present invention is to provide a method for manufacturing galvanized metal sheets that requires extremely short processing time.

本発明により、 水溶性のＣｏ、Ｎｉ　　或いはＭｏ化合物の１種以上を
、金員としてＣｏ、Ｎｉについては３〜５ｏｆ／ｆｔ１
Ｍ０ニつイテハα０１〜３ｔ／２添加したＺｎを主成分
とする酸性電気亜鉛めっき浴中で金属板を電気亜鉛めっ
きした後、同一浴中で電気量５〜５００クーロン／ｄ−
の陽極電解処理（第１処理）を施す事を特徴とする着色
電気亜鉛めっき金属板の製造法および水溶性のＣｏ　、
　Ｎｉ或いはＭｏ化合物の１種以上を、金属としてＣｏ
、Ｎｉにつぃ゛ては３〜５ｏφ、Ｍｏについてはα０１
〜３　ｔｌｉ、添加したＺｎを主成分とする酸性電気亜
鉛めっき浴中で金属板を電気亜鉛めっきした後、同一浴
中で電気ｉｉ５〜５００クーロン／ｄｗｔの陽極電解処
理（第１処′理）を施し、ついで重クロム酸及び／又は
重クロム酸塩を５〜１００　ｔ／ｉＬ含む浴中で電気量
５〜５００クーロン／ｄｏｔの陰極電解処理（第２処理
）を施す事を特徴とする着色電気亜鉛めっき金属板の製
造法が提供される。According to the present invention, one or more of water-soluble Co, Ni or Mo compounds is added as a metal in an amount of 3 to 5 of/ft1 for Co and Ni.
After electrogalvanizing a metal plate in an acidic electrogalvanizing bath mainly containing Zn added with M0 Nitteha α01~3t/2, the amount of electricity is 5~500 coulomb/d- in the same bath.
A method for producing a colored electrogalvanized metal sheet characterized by subjecting it to an anodic electrolytic treatment (first treatment) of water-soluble Co,
One or more types of Ni or Mo compounds and Co as a metal
, 3~5oφ for Ni, α01 for Mo
~3tli, after electrogalvanizing a metal plate in an acidic electrogalvanizing bath containing added Zn as a main component, anodic electrolytic treatment at an electric current of 5 to 500 coulombs/dwt (first treatment) in the same bath. coloring, followed by cathodic electrolytic treatment (second treatment) with an amount of electricity of 5 to 500 coulombs/dot in a bath containing 5 to 100 t/iL of dichromic acid and/or dichromate. A method of manufacturing an electrogalvanized metal sheet is provided.

以下に本発明の詳細な説明する。The present invention will be explained in detail below.

水溶性のコバルトおよび／もしくはニッケルおよび／も
しくはモリブデンの化合物を含有する亜鉛を主成分とす
る心中で金属板を電気めつきすると、当然ながらめつき
１−には亜鉛の他にコバルトおよび／もしくはニッケル
および／もしくはＭ。When a metal plate is electroplated in a zinc-based core containing water-soluble cobalt and/or nickel and/or molybdenum compounds, plating 1- naturally contains cobalt and/or nickel in addition to zinc. and/or M.

が共析する。そこでこの電気亜鉛めっきした金−板をめ
っき液中で陽極電解処理（第１処理）すると、亜鉛表面
に存在するＣｏ、　Ｎｉ、　Ｍｏのいづれか１種以上が
優先的に酸化され青黒色乃至黒色の表面を呈するように
なる。この現象は従来の単なる°電気亜鉛めっき金属板
の陽極電解処理によっては境われ得ないもので、発色体
となるべき前記共析金属の存在が必要不６■欠である。is eutectoid. Therefore, when this electrogalvanized gold plate is subjected to anodic electrolysis treatment (first treatment) in a plating solution, one or more of Co, Ni, and Mo present on the zinc surface is preferentially oxidized, resulting in a blue-black to black color. begins to appear on the surface. This phenomenon cannot be overcome by a simple conventional anodic electrolytic treatment of electrogalvanized metal sheets, and the presence of the eutectoid metal that serves as a color former is essential.

本発明は、基本的には特開昭５５−９１９９３号及び特
開昭５６−２９３号の明細軒ｔユ記載された発明を更に
改良したものである。すなわち、本発明は電気番組めっ
きをする液を用いてめっき後の金属板を陽極電解処理（
第１処理）することによって−常に短時間にめつき金属
板を暗色着色させると云う新規知見に基づいて、初めて
所期の効果を納め得たものである。The present invention is basically a further improvement of the invention described in the specifications of JP-A-55-91993 and JP-A-56-293. That is, the present invention uses an electroplating solution to subject a plated metal plate to an anodic electrolytic treatment (
The desired effect was achieved for the first time based on the new knowledge that a plated metal plate can always be colored darkly in a short period of time by carrying out the first treatment.

ここに基体金属板は、スケールを除去した熱延鋼板、冷
延鋼板、亜鉛めっき鋼板、ふりき、酌めつき鋼板、Ｃｏ
めつき鋼板、ステンレス鋼板等の鋼板の他、　Ｃｗまた
はＣｕ合金板、ＡｌｌまたはＡ１合金板等の各種非鉄金
属板であることが出来る。Here, the base metal sheet is a hot-rolled steel sheet from which scale has been removed, a cold-rolled steel sheet, a galvanized steel sheet, a furiki, a tinted steel sheet, a Co
In addition to steel plates such as plated steel plates and stainless steel plates, various nonferrous metal plates such as Cw or Cu alloy plates, All or A1 alloy plates, etc. can be used.

本発明に於て、めっき浴組成のうちの添加元素及び有機
添加剤の量及び陽極亀解処！Ｍ（第１処理）電気量を限
定しているのは次の理由によるものである。すなわち、
コバルト及び／又はニッケルの化合物成分は金属として
３〜５　Ｑ　ｔｌｉの範囲が望ましく、３のよりも少い
と陽極電解処理（第１処＠）しても発色し難いからであ
り、また５　９　ｆ／１より多いとめつき作業が困難と
なり、かつ、めっき性も悪くなるためである。コバルト
及び／又はニッケル化合物の特に’Ｊｌましい成分は経
験上金属として５〜２０　ｆ／Ｉｔである。In the present invention, the amount of additive elements and organic additives in the plating bath composition and the anodic electrolyte treatment! The reason why the amount of electricity M (first process) is limited is as follows. That is,
The compound component of cobalt and/or nickel is desirably in the range of 3 to 5 Qtli as a metal, because if it is less than 3, it will be difficult to develop color even if the anodic electrolytic treatment (first treatment @) is carried out, and 59 f This is because if the amount is more than /1, the plating work becomes difficult and the plating performance deteriorates. A particularly desirable component of the cobalt and/or nickel compound is 5 to 20 f/It based on experience as a metal.

また、ＭＯの化合物は金属として０．Ｏ１〜３　ｔｌｉ
の範囲が望ましい。その理由は０．０１　ｔｌｉ　Ｂ下
の場合は発色効果が小さく　、　３　ｔ、Ａ以上ではめ
つき層の密着性が低下するからである。Moreover, the compound of MO is 0.0% as a metal. O1~3 tli
A range of is desirable. The reason for this is that below 0.01 tli B, the coloring effect is small, and above 3 t, A, the adhesion of the plating layer decreases.

更に、発色後の外観を良くするための手段の１つとして
めっき層自体を寂える方法がある。すなわち、めっき浴
に有機添加剤を添加することにより後処理や塗装等によ
らずとも陽極電解処理（第１処理）によって青黒色化乃
至黒色化を促進し、美麗な着色亜鉛めっき金属板を得る
ことが出来るのである。勿論これに加えて後処理や塗装
を施せば美感は更に増すことはいう迄もない。適当な有
機添加剤としては、水溶性もしくは水分敵性のポリアク
リレート共重合体、ジシアンジアミド・ホルムアルデヒ
ド、ポリビニルアルコール或いはカチオン性ポリアミン
の各有機化合物があり、めっき浴中にこれらの有機添加
剤の少くともｌ柚以Ｅを合計０．１〜１０　ｔ／Ｉｔ添
加すれば、濃い青黒色乃至黒色の美麗なめつき表面が得
られる。添加瀘はａ　１　ｆＡより少なければ効果がな
く、１０　ｆ／１２を超えるとめっき性が悪くなるから
上記範囲が艮い。Furthermore, one way to improve the appearance after color development is to reduce the plating layer itself. That is, by adding organic additives to the plating bath, blue-black or blackening is promoted through anodic electrolytic treatment (first treatment) without post-treatment or painting, thereby obtaining a beautiful colored galvanized metal sheet. It is possible. Of course, it goes without saying that if you apply post-treatment and painting in addition to this, the aesthetic appearance will further increase. Suitable organic additives include water-soluble or water-friendly organic compounds such as polyacrylate copolymers, dicyandiamide formaldehyde, polyvinyl alcohol, or cationic polyamines, and at least 1 of these organic additives are present in the plating bath. If Yuzui E is added in a total amount of 0.1 to 10 t/It, a beautiful glossy surface of deep blue-black to black color can be obtained. The additive filter is ineffective if it is less than a 1 fA, and if it exceeds 10 f/12, the plating properties deteriorate, so the above range is not acceptable.

また、共析亜鉛めっきに引き続いての上記浴中での陽極
電解処理（第１処理）は電気量５〜５００’）　−ｔｆ
ｆ　ｙ％−が望ましい。電気量が５クーｏ　ｙ　／　ｄ
ｍ以下の場合には発色効果が小さく、５００クーロン／
ａｄを超えると処理膜の密着性に問題を生じ・るととも
に、ムが陽極処理電気量に比例して再溶解するため経済
的でない。Further, the anodic electrolytic treatment (first treatment) in the above bath following the eutectoid galvanizing has an electric charge of 5 to 500') -tf
f y%- is desirable. The amount of electricity is 5 y/d
m or less, the coloring effect is small, and 500 coulombs/
If it exceeds ad, problems will arise in the adhesion of the treated film, and it will be uneconomical because the mu will be redissolved in proportion to the amount of electricity used in the anodic treatment.

これらの青黒色化乃至黒色化した共析電気亜鉛めっき金
属板の裸耐食性は、概して弱い腐食性雰囲気においては
良好である（恒温多湿試験）が、塩水噴霧試験ではやや
もの足りない。例えば目付量Ｉ　Ｑ　ｆ／ｈｌの場合、
恒温多湿試験では５０日経過後も全く変化がなく良好で
あるが塩水噴霧試験では３８時間で白錆が発生した。The bare corrosion resistance of these blue-black or blackened eutectoid electrogalvanized metal sheets is generally good in a weakly corrosive atmosphere (constant temperature and humidity test), but is somewhat unsatisfactory in a salt spray test. For example, in the case of the basis weight I Q f/hl,
In the constant temperature and high humidity test, there was no change at all even after 50 days, which was good, but in the salt spray test, white rust occurred after 38 hours.

なお、更に青黒色乃至黒色表面を深みのあるものとして
美観を上げ、加えて耐食性向上を図る手段としてめっき
、陽極電解処理（ｊｌ！１処理）後の表面に珪酸系処理
をする方法と透明もしくは半透明の合成樹脂塗膜を施−
［方法がある。In addition, as a means to enhance the beauty of the blue-black or black surface by giving it a deep appearance, and to improve corrosion resistance, there is a method in which the surface is treated with silicic acid after plating and anodic electrolytic treatment (JL!1 treatment), and transparent or Applying semi-transparent synthetic resin coating
[There is a way.

珪酸系処理とは、珪酸またはリチウムシリケート、カリ
ウムシリケート、ナトリウムシリケート等の珪酸塩乃至
これらの混合物の水溶液（必要に応シて更にクロム酸又
はクロム酸塩もしくハコレらの混合物を加える）を前記
青黒色化乃全黒色化した共析電気亜鉛めっき表面に例え
ば浸漬、スプレー塗装、ロール塗装その他の手段で塗布
し乾燥することであるっこの場合付雪量（塗布膜量）は
珪素として測定して乾燥後において１０〜４０ｏＩＩＶ
％Ｉｒどなるように壁布することが重要である。すなわ
ち珪素付装置が１０　撃宿よりも少いと効果がなく、４
００榮臂を超えると処理膜の密着性に間融な生じるから
である。The silicic acid treatment refers to an aqueous solution of silicic acid or a silicate such as lithium silicate, potassium silicate, sodium silicate, or a mixture thereof (if necessary, chromic acid or a chromate or a mixture of chromates or the like is added) to the above-mentioned. It is applied to the blue-black or completely black eutectoid electrogalvanized surface by, for example, dipping, spray painting, roll painting, or other means, and then dried. In this case, the amount of snow deposited (coated film amount) is measured as silicon. 10-40oIIV after drying
%Ir It is important to make the wall cloth as it is. In other words, if the silicone attachment device is less than 10, it is ineffective, and 4
This is because if it exceeds 0.00, the adhesion of the treated film will deteriorate.

なお珪酸系処理は上記の他、特公昭４４−１９６８６号
乃至特公昭４５−５１３０号明細書記戦のように珪酸ま
たは硅酸塩の他にリン酸またはリン酸塩乃至は水溶性も
しくは水分散性の有機尚分子を含む水溶液の塗布によっ
ても得ることが出来−る。In addition to the above-mentioned silicic acid treatment, in addition to silicic acid or silicates, phosphoric acid or phosphates or water-soluble or water-dispersible It can also be obtained by coating an aqueous solution containing organic molecules.

また、−極電解処理（第１処理）後に施す透明乃至半透
明の塗膜は、各種の天然樹脂または合成樹脂を水または
有機溶剤で希釈して塗布し乾燥することにより得られる
。これらの樹脂塗料は例えばボイル油、油ワニス、揮発
性乾燥ワニス、シェラツクワニス、ラッカー、フェノー
ル樹脂ワニス、フタ＃［樹脂ワニス、尿素樹脂ワニス、
メラミン樹脂ワニス、酢酸ビニル・アクリル樹脂ワニス
、スチレン化アルキッド、樹脂ワニス等である。塗布方
法は浸漬、スプレー塗装、ロール塗装その他が用いられ
る。The transparent to semitransparent coating film applied after the -electrode electrolysis treatment (first treatment) can be obtained by diluting various natural or synthetic resins with water or an organic solvent, applying the diluted solution, and drying the coating. These resin paints include, for example, boiled oil, oil varnish, volatile dry varnish, shell varnish, lacquer, phenolic resin varnish, lid # [resin varnish, urea resin varnish,
These include melamine resin varnish, vinyl acetate/acrylic resin varnish, styrenated alkyd, resin varnish, etc. Application methods include dipping, spray coating, roll coating, and others.

上述の珪酸系処理乃至樹脂塗料塗布を行なうと仕上がり
後の亜鉛めっき表面が深みを帯びた青黒色乃至黒色とな
り美観を増すと共に後述の実施例に示すとおり耐食性も
向上する。When the above-mentioned silicic acid treatment or resin coating is applied, the finished galvanized surface becomes deep blue-black or black, improving the aesthetic appearance and improving corrosion resistance as shown in the examples below.

また、陽極電解処理（ＩＪ１処理）後に施す重クロム酸
および／又は重クロム酸塩中での陰極電解処理（１＄２
処理）は電気１５〜５００　クーａ　ｙ７ａｄが望まし
い。５ク一ロン／ｄｗＩ以下では耐食性向上に効果が小
さく、また５０ｏクーロン／ｄ−以上は経済的でない。In addition, cathodic electrolytic treatment in dichromic acid and/or dichromate (1$2
Treatment) is preferably conducted at an electric power of 15 to 500 y7ad. If it is less than 5 coulombs/dwI, the effect of improving corrosion resistance is small, and if it is more than 50 coulombs/dwI, it is not economical.

これらの他、重クロム酸および／又は亀クロム酸塩溶液
中での陰極電解処理（第２処理）後上述した珪酸系処理
ないＬ７透明もしくは半透明の合成樹脂塗膜を更に施す
方法もある。これらの処理条件は既に記した範囲が望ま
しい。In addition to these, there is also a method of further applying a L7 transparent or translucent synthetic resin coating without the above-mentioned silicic acid treatment after cathodic electrolytic treatment (second treatment) in a dichromic acid and/or torochromate solution. These processing conditions are preferably within the ranges already described.

以上述べたとおり、本発明を実施することにより、比較
的簡単な処、理で色ムラのない暗色着色亜鉛めっき金鵬
板を得ることが出来る。すなわち前記の目的のすべてを
達成できる。従って本発明の工業的価値は著るしく大き
いものである。As described above, by carrying out the present invention, it is possible to obtain a dark colored galvanized gold plate with no color unevenness through relatively simple processing. In other words, all of the above objectives can be achieved. Therefore, the industrial value of the present invention is significantly large.

なお、基体金−板は各種加工金属板、もしくは金属製品
であってもよいことは云う迄もない。It goes without saying that the base metal plate may be any of various processed metal plates or metal products.

以下に実施例を示す。Examples are shown below.

実施例１ 板厚α４ｔ４）軟鋼板を７％苛性ソーダ水溶液中で電解
脱脂した後水洗し、次に７０　ｆ／Ｉｔの硫酸で酸洗を
行った後水洗し、めっき原板とした。前記処理によっ゛
て得られた原板を以下の条件でめっきした。Example 1 Plate thickness α4t4) A mild steel plate was electrolytically degreased in a 7% caustic soda aqueous solution and washed with water, then pickled with 70 f/It sulfuric acid and washed with water to obtain a plating original plate. The original plate obtained by the above treatment was plated under the following conditions.

めっき浴組成 Ｚｎ８０４−７Ｈ２０２５０ｔ／１゜ （ＮＨ４）り・８０４　　　　　　　　　　　１５　　
ｔ／１１ＣＯ８０４・７Ｈり０　（ＣＯとして）　　　
　　Ｓｔ／Ｉｔジシアンジアミド・ホルムアルデヒド　
　　　　　１　　ｆ／Ｉｔめつき浴温　　　　３８℃ 電流密度　　　　　２５　Ａ／ｄ＋＋／めっき量　　　
　　１０　ｆ／Ｍｌ 得られたＣｏを含む亜鉛めっき銅板を、引き続き上記め
っき浴中で、めっき鋼板を陽極として電気量４０クーロ
ン／ｄｗｌの電解処理（第１処理）を施し更に、濃度５
００　ｖ／１１のリチウムシリケート溶液（Ｌｉ＊Ｏ：
　８ｔ（ｈ■１：４）に３秒間浸漬した後乾燥後におい
て珪素としての付着量が２００−となる嫌にロールコー
トした後ホットドライヤーで乾燥した。Plating bath composition Zn804-7H20250t/1°(NH4)ri・804 15
t/11CO804・7Hri0 (as CO)
St/It dicyandiamide formaldehyde
1 f/It plating bath temperature 38℃ Current density 25 A/d++/plating amount
10 f/Ml The obtained galvanized copper plate containing Co was then subjected to an electrolytic treatment (first treatment) in the above plating bath with the galvanized steel plate as an anode at an amount of electricity of 40 coulombs/dwl.
00 v/11 lithium silicate solution (Li*O:
After being immersed in 8t (h 1:4) for 3 seconds and dried, the film was roll coated so that the amount of silicon deposited was 200 -, and then dried with a hot dryer.

得られた試料は美麗な濃い青黒色乃至黒色を呈し、セロ
ファンテープ剥離試験でも皮膜の剥離はなかった。又、
ＪＩＳ　Ｚ　２３７１によｉ塩水噴霧試験において、連
続２４時間経過後全く変化なかった。The obtained sample exhibited a beautiful deep blue-black to black color, and the film did not peel off even in a cellophane tape peeling test. or,
In the salt water spray test according to JIS Z 2371, there was no change at all after 24 continuous hours.

実施例２ 実施例１と同様に脱脂、酸洗を行っためっき原板を以下
の条件でめっきした。Example 2 A plating original plate that had been degreased and pickled in the same manner as in Example 1 was plated under the following conditions.

めっき浴組成 Ｚｎ８０ａ・７Ｈ２０２５０ｆ／１１ （ＮＨ４）２８０１　　　　　　　　　１５　ｆ／１１
Ｎｉ８０４・７Ｈ２０（Ｎｉとして）　　　　Ｂｔ７ｔ
ｈポリビニルアルコール　　　　　　　　　　　　　２
　　ｔ／ｊ！めつき浴温　　　　５０℃ 電流密度　　　　　２５　Ａ／ｄｗｔ めっき量　　　　　１５ｆ／♂ 得られたＮｉを含む亜鉛めっき鋼板を、引き続き、上記
浴中で、嘔気［１００クーロン／ｄｓ’の陽極電解処理
（ＩＪＩ処理）を施し、更に実施例１と同様の方法でリ
チウムシリケートな塗布した。Plating bath composition Zn80a/7H20250f/11 (NH4)2801 15 f/11
Ni804・7H20 (as Ni) Bt7t
h polyvinyl alcohol 2
t/j! Plating bath temperature: 50°C Current density: 25 A/dwt Plating amount: 15 f/♂ The obtained galvanized steel sheet containing Ni was subsequently subjected to anodic electrolysis treatment (IJI treatment) at 100 coulombs/ds' in the above bath. was applied, and lithium silicate was further applied in the same manner as in Example 1.

得られた試料は美麗な濃い青黒色乃至黒色を呈し、セロ
ファンテープ剥離試験での皮膜の剥離はなく、ＪＩＳ　
Ｚ　２３７１による塩水噴霧試験において連続２４時間
経過後全く変化なかった。The obtained sample exhibited a beautiful deep blue-black to black color, and there was no peeling of the film in the cellophane tape peeling test, and the JIS
In the salt spray test using Z 2371, there was no change at all after 24 continuous hours.

実施例３ 実施例１と同様に脱脂、酸洗しためっき原板を以下の条
件でめっきした・ めっき浴組成 Ｚｎ８０ｍ４Ｈｓ０　　　　　　　２５０　ｔ／１１（
ＮＨ４）　ａ８０ａ　　　　　　　　　　　１５　　ｆ
／ＩＬＣＯ８０４・７ＨｓＯ（Ｃｏとして＞　　　　８
ｔ／ｊｌめつき浴温　　　　　４５℃ 電流密度　　　　　　２５　Ａ／ｄｍ″めっき量　　　
　　　１５　ｔ／ｍｌ 得られたＣｏを含む亜鉛めっき鋼板を、引き続き上記浴
中で、電気量１００クーロン／ｄｗｔの陽極電解処理（
第１処理）を施し、更に濃度５００　ｔＡ　ｏ＞カツク
ムシリケート溶液（Ｋ：８ｉ（ｈ−１：４）に３秒間浸
漬した後乾燥後において珪素としての付着量が２００−
となる様にロールコートした後ホットドライヤーで乾燥
した。Example 3 A plating original plate that had been degreased and pickled in the same manner as in Example 1 was plated under the following conditions: Plating bath composition Zn80m4Hs0 250t/11 (
NH4) a80a 15 f
/ILCO804・7HsO (as Co>8
t/jl Plating bath temperature 45℃ Current density 25 A/dm'' plating amount
15 t/ml The obtained galvanized steel sheet containing Co was subsequently subjected to an anodic electrolytic treatment (
1st treatment), and further immersed in a concentration of 500 tA o>Katsukum silicate solution (K: 8i (h-1:4) for 3 seconds, and after drying, the amount of silicon deposited was 200-
After roll coating, it was dried with a hot dryer.

得られた試料は美麗な青黒色乃至黒色を呈し、セロファ
ンテープ剥離試験でも皮膜の剥離はなべ、ＪＩ８　Ｚ　
２３７１による塩水噴霧試験において連続２４時間経過
後も全く変化なかった。The obtained sample exhibited a beautiful blue-black to black color, and the film did not peel off even in the cellophane tape peel test.
In the salt water spray test using 2371, there was no change at all after 24 continuous hours.

実施例４　　　　一 実施例１と同様に脱脂、酸洗しためつき原板を以下の条
件でめっきした。Example 4 In the same manner as in Example 1, a degreased and pickled original plate was plated under the following conditions.

めっき浴組成 Ｚｎ８０４・７Ｈ２０２５０ｔ／１１ （ＮＨａ）ｓ８０４２０　ｔ／１１ ＣＯ８０４・７Ｈ２０（Ｃｏとして）　　　　８　ｆ／
ｉ（ＮＨ４）６ＭＯ７０２４・４Ｈ２００，１ｔ／Ｌ電
流密度　　　　　２５　ｋ／ｄｙｌ めっき量　　　　　２０　ｔ／♂ 得られたＣｏ　、　Ｍｏを含む亜鉛めっき鋼板！引き続
き上記浴中で電気量２００クーロン／ｄ−の陽極°電解
処理（第１処理）を施し更に、５　ｆ／蘇のＣｒｙｓを
含む濃度５ｏｏｒ／ｎのリチウムシリケート溶液に３秒
間浸漬し、乾燥後において珪素としての付嵩量が２ｏｏ
号省となる様にロールコートした後、ホットドライヤー
で乾燥した。Plating bath composition Zn804・7H20250t/11 (NHa)s80420t/11 CO804・7H20 (as Co) 8f/
i(NH4)6MO7024・4H200, 1 t/L Current density 25 k/dyl Coating amount 20 t/♂ The obtained galvanized steel sheet containing Co and Mo! Subsequently, it was subjected to anodic electrolytic treatment (first treatment) with an electric charge of 200 coulombs/d in the above bath, and then immersed for 3 seconds in a lithium silicate solution containing 5 f/s of Crys at a concentration of 5 oor/n, and after drying. The bulk amount as silicon is 2oo in
After roll-coating it to give the desired color, it was dried with a hot dryer.

得られた試料は美麗な濃い青黒色乃至黒色を呈し、セロ
ファンテープ剥離試験で皮膜の剥、離はなかった。又Ｊ
Ｉ８Ｚ　２３７１による塩水噴霧試験連続２４時間経過
後も全く変化なかった。The obtained sample exhibited a beautiful deep blue-black to black color, and there was no peeling or separation of the film in the cellophane tape peeling test. Also J
There was no change at all even after 24 hours of continuous salt spray testing using I8Z 2371.

実施例５ 実施例１と同様に脱脂、酸洗を行つためつき原板を以下
の条件でめっきした。Example 5 A plated base plate for degreasing and pickling was plated under the following conditions in the same manner as in Example 1.

めっき浴組成 １ｍ８０ａ・７Ｈ冨０　　　　　　　２５０　ｔ／１１
Ｎｉ８０ａ・７ＨｔＯ（Ｎｉとして）８Ｆ／４１（ＮＨ
ａ　）雪８０４　　　　　　　　　１５　ｔ／１１めっ
き浴温　　　　　４０’Ｃ 電流密度　　　　　　２５人／ｄＷｌ めっき量　　　　　　２０　ｆ／Ｉｌｉ！’得られたＮ
ｉを含む亜鉛めっき鋼板を上記めっき浴中で電気量４０
０クーロン／ｄＷｔの陽極電解処理（第１＠理）し、次
いで透明の合成樹脂塗料（商品名カンペクツヤーラッカ
ー）をスプレ′−塗布した。Plating bath composition 1m80a・7H depth 0 250t/11
Ni80a・7HtO (as Ni) 8F/41 (NH
a) Snow 804 15 t/11 Plating bath temperature 40'C Current density 25 people/dWl Plating amount 20 f/Ili! 'Obtained N
A galvanized steel sheet containing i was heated in the above plating bath with an electric charge of 40
It was subjected to an anodic electrolytic treatment (first treatment) at 0 coulombs/dWt, and then a transparent synthetic resin paint (trade name: Kanpekutsuya Lacquer) was spray-coated.

得られた試料は美麗な青黒色乃至黒色を呈し、セロファ
ンテープ剥離試験で皮膜の剥離はなかった。The obtained sample exhibited a beautiful blue-black to black color, and no peeling of the film occurred in the cellophane tape peeling test.

又ＪＩ８　Ｚ　２３７１塩水噴霧試験において連続２４
時間経過後も全く変化なかった。Also, in the JI8 Z 2371 salt spray test, continuous 24
There was no change at all after the passage of time.

実施例６ 実施例１と同様に脱脂、酸洗を行っためっき原板を以下
の条件でめっきした。Example 6 A plating original plate that had been degreased and pickled in the same manner as in Example 1 was plated under the following conditions.

めっき浴組成 Ｚｎ８０４４Ｈ２０２５０ｔ／１１ （ＮＨ４）２８０４　　　　　　　　　　□５１／Ｊｌ
Ｃｏ８０４・７Ｈ２０（Ｃｏとして）　　　　　　５　
　ｔ／１ｔＮｉ８０４７ＨｚＯ（Ｎｉとり、て）　　　
　　　５　　ｔ／１１ジシアンジアミド・ホルムアルデ
ヒド　　　　　　　ｌ　　ｆ／Ｉｔめつき浴温　　　　
　３８℃ 電流密度　　　　　　２５　Ａ／ｄ♂ めっき量　　　　　　２０　ｔ／Ｍｌ 得られたＣｏ、Ｎｉを含む亜鉛めっき鋼板を上記めっき
浴中で電気［２００クーロン／Ｕの陽極電解処理（第１
処理）を施し更に、重クロム酸ナトリウム３０ｆ４を含
′む浴中で温度４０℃で電気１１Ｌ１００りｉロン／ｄ
ｄの陰極処理（第２処理）を施し、次で実施例１と同様
の方法でリチウムシリケートを伏布した。Plating bath composition Zn8044H20250t/11 (NH4)2804 □51/Jl
Co804・7H20 (as Co) 5
t/1tNi8047HzO (Ni, Te)
5 t/11 dicyandiamide/formaldehyde l f/It plating bath temperature
38°C Current density 25 A/d♂ Coating amount 20 t/Ml The obtained galvanized steel sheet containing Co and Ni was subjected to electric [200 coulomb/U anodic electrolytic treatment (first
treatment), and then heated in a bath containing 30 f4 of sodium dichromate at a temperature of 40°C with an electric current of 11 L, 100 L/d.
The cathode treatment (second treatment) of d was performed, and then lithium silicate was applied in the same manner as in Example 1.

得られた試料は美麗な濃い青黒色乃至黒色を呈し、セロ
ファンテープ剥離試験での皮膜の剥ｌｌはなく、ＪＩ８
Ｚ！３７１による塩水噴霧試験において、連続２４時間
経過後も全く変化なかった。The obtained sample had a beautiful deep blue-black to black color, and there was no peeling of the film in the cellophane tape peeling test, and it was JI8.
Z! In the salt spray test using No. 371, there was no change at all after 24 continuous hours.

比較例１ 実施例１と同様に脱脂、酸洗を行つためつき原板を以下
の条件でめっきした。Comparative Example 1 A plated original plate for degreasing and pickling was plated under the following conditions in the same manner as in Example 1.

めっき浴組成 Ｚｗｒ８０４４Ｈ意０　　　　　　　　２５０　　ｔ７
！−（ＮＨａ　）意８０４　　　　　　　　　１５　ｆ
／１電流密度　　　　　　　２５　Ａ／ｄＭｌめっき量
　　　　　　　１０　ｔ／ｄ 得られたＣＯを含む亜鉛めっき鋼板は灰色を呈し、セロ
ファンテープ剥離試験での皮膜剥離はなかったがＪＩ８
２２３７１による塩水噴霧試験においで２４時間経過後
は全面白赤錆が発生していた。Plating bath composition Zwr8044Hi0 250 t7
! -(NHa) 804 15 f
/1 Current density 25 A/dMl Coating amount 10 t/d The obtained galvanized steel sheet containing CO had a gray color, and there was no peeling of the film in the cellophane tape peeling test, but JI8
In the salt water spray test using No. 22371, white-red rust had occurred on the entire surface after 24 hours.

比較例２ 実施例１と同様に脱脂、酸洗を行つためつき原板を以下
の条件でめっきした。Comparative Example 2 A plated original plate for degreasing and pickling was plated under the following conditions in the same manner as in Example 1.

めっき浴組成 Ｚｎ８０４４Ｈｚ０　　　　　　　２５０　ｆＩＱ（Ｎ
Ｈ４）２８０４　　　　　　　　　　１５　　ｆ／ＩＣ
０８０４・７Ｈ２０（Ｃｏとして）　　　　　　Ｂ　　
ｔ７ｔｈ（ＮＨａ）ｉＭｏｙＯｚ＋・４Ｈ２００，１ｆ
／ｊ！電流密度　　　　　　２５　ｋ／ｄｖｔめっき量
　　　　　　１ｏ　ｔ／ｗｌ 得られたＣｏ、　Ｍｏを含む亜鉛めっき一板は光沢のあ
る淡黄色を呈し、セロファンテープ剥離試験での皮膜の
剥離はなかったが、ＪＩ８　Ｚ　２３７１による塩水噴
霧試験において２４時間経過後は全面白赤錆が発生して
いた。Plating bath composition Zn8044Hz0 250 fIQ(N
H4) 2804 15 f/IC
0804・7H20 (as Co) B
t7th(NHa)iMoyOz+・4H200,1f
/j! Current density: 25 k/dvt Plating amount: 1 ot/wl The resulting galvanized sheet containing Co and Mo exhibited a glossy pale yellow color, and there was no peeling of the film in the cellophane tape peeling test, but JI8 Z 2371 After 24 hours, white-red rust had formed on the entire surface of the product in a salt spray test conducted by the company.

比較例３ 実施例１と′同様に脱脂、酸洗を行っためっき原板を以
下の条件でめっきした。Comparative Example 3 A plating original plate that had been degreased and pickled in the same manner as in Example 1 was plated under the following conditions.

めっき浴組成 Ｚｎ８０ｎ４Ｈｚ０　　　　　　　２５０　ｔ／１（Ｎ
Ｈ４）ｉ８０ａ　　　　　　　　　　１５　ｆＩＱ。Plating bath composition Zn80n4Hz0 250t/1(N
H4) i80a 15 fIQ.

めっき温度　　　　　４０℃ 電流密度　　　　　　２５　ｋ／ｄｗｌめっき量　　　
　　　２０　ｆ／ＩＩＦ得られた亜鉛めっき銅板を上記
めっき浴中で電気量１００クーロンＺ塚の陽極電解処理
（第１処ｆｉ）を施した。得られた試料は灰色を呈し、
セロファンテープ剥離試験での皮膜の剥離はなかったが
、ＪＩ８２２３７１による塩水噴霧試験においては、２
４時間経過後は全面白赤錆が発生していた。Plating temperature 40℃ Current density 25 k/dwl plating amount
20 f/IIF The obtained galvanized copper plate was subjected to anodic electrolytic treatment (first treatment fi) in the above plating bath at an electric charge of 100 coulombs. The obtained sample has a gray color,
There was no peeling of the film in the cellophane tape peeling test, but in the salt spray test according to JI822371, 2
After 4 hours, white-red rust had formed on the entire surface.

以・下実施例を第１表にまとめて示す。The following examples are summarized in Table 1.

特許出願人　東洋鋼鈑株式会社Patent applicant: Toyo Kohan Co., Ltd.

Claims (1)

【特許請求の範囲】 （１）　　水溶性のＣｏ、　Ｎｉ或いはＭｏ化合物の１
種以上を、金属としてＣｏ、　Ｎｉについては３〜５０
　ｆ／Ｉｔ　。 腸については０．０１〜３　ｔ７ｔｔ添加したＺｎを主
成分とする酸性電気亜鉛めっき浴中で金属板を電気曲鉛
めっきした後、同一浴中で電気祉５〜５００クーロン／
ｄｗｌの陽極電解処理（第１処理）を施す拳を特徴とす
る着色電気亜鉛めっき金属板の製造法。 （り　前記酸性′磁気亜鉛めっき浴が、更に水溶性もし
くは水分散性のポリアクリレート共重合体、ジシアンジ
アミド・ホルムアルデヒド、ポリビニルアルコール或い
はカチオン性ポリアミンの各有機化合物の少くとも１種
以上を合計０．１〜１０ｆＡを含む浴である特許請求の
範囲第１項記載のめつき金属板の製造法。 （讃　前記陽極電解処理（第１処理）後のめつき金属板
に、更に珪酸及び／又は珪酸塩及び／又はクロム酸及び
／又はクロム酸塩を含む水浴液を乾燥後の珪素付線−が
１０〜４００−４／ｌｌとなるように塗布する特許請求
の範ｌｌｌ１第１項乃至第２項Ｏ）シ）づれか１項に記
載のめつき金属板の製造法。 （４）　　前記陽極電解処理（第１処理）僅のび机板を
水洗乾燥し、ついで樹脂塗料Ｙ　螢１１Ｊすることシ二
よって透明乃至半透明の塗膜を施工特許請求の範囲第１
項乃至第３項の内いづれか１項に記載Ｑ）めっき金属板
の製造法１、 （９前記金属板が銅板もしくは各檀非鉄金属板である特
許請求の範囲第１項乃至第４項のいづれか１項に記載の
めつき金属板の製造法。 （６）　　水溶性のＣｏ、Ｎｉ或いはＭｏ化合物の１種
思−ヒを金属としそＣｏ、Ｎｉについては３〜５０９７
Ｍ　、Ｍ（＋については０．０１　’−３ｙ／Ｉｔ添加
した７１＞　ｆ主成分とする酸性電気亜鉛めつき浴中で
金属板を礒気曲船めっきした後、同一浴中で磁気−５〜
５００クーロン／ｄゼの陽極電解処理（第１処理）を施
し、ついで重クロム酸及び／又は重クロム酸塩を５〜１
００　ｆＡ含む浴中で電気祉５〜５００クーロン／ｄ♂
の陰極電解処理（第２処理）を施す事を特徴とする着色
電気亜鉛めっき金属板の製造法。 （力　前記酸性電気亜鉛めっき浴が、更に水溶性もしく
は水分散性のポリアクリレート共重合体、ジシアンジア
ミド・ホルムアルデヒド、ポリビニルアルコール或いは
カチオン性ポリアミンの各有機化合物の少くとも１種以
上を合計０．１〜ｌ　Ｑ　ｆ／ｎを含む浴である特許請
求の範囲第６項記載のめつき金属−の製造法。 （６）前記陰極電解処理（第２処理）後のめつき金属板
に、更に珪酸及び／又は珪酸塩及び／又はクロム酸及び
／又はクロム酸塩を含む水溶液を乾燥後の珪素付着量が
１０〜４００　ａｐＡｄとなるよ、うに塗布する特許請
求の範囲第６項乃至第７項のいづれか１項に記載のめつ
き金属板の製造法。 ■　前記陰極電解処理（第２処理）後の金属板を水洗乾
燥し、ついで樹脂塗料を塗布することによって透明乃至
半透明の塗膜な施工特許請求の範囲第６項乃至第８項の
内いづれか１項に記載のめつき金属板の製造法。 叫　前記金属板が鋼板もしくは各種非鉄金属板である特
許請求の範囲第６項乃主第９墳のいづれか１項に記載の
めつき金属板の製造法。[Claims] (1) One of water-soluble Co, Ni or Mo compounds
3 to 50 for Co and Ni as metals
f/It. For the intestine, after electroplating the metal plate in an acidic electrogalvanizing bath containing Zn as the main component to which 0.01 to 3 t7tt was added, an electric flux of 5 to 500 coulombs/galvanization was applied in the same bath.
A method for producing a colored electrogalvanized metal sheet characterized by a fist subjected to dwl anodic electrolysis treatment (first treatment). (i) The acidic magnetic galvanizing bath further contains at least one of a water-soluble or water-dispersible organic compound such as a polyacrylate copolymer, dicyandiamide/formaldehyde, polyvinyl alcohol, or a cationic polyamine in a total of 0.1 A method for manufacturing a plated metal plate according to claim 1, wherein the bath contains 10 fA. and/or applying a water bath solution containing chromic acid and/or chromate so that the silicon bonded wire after drying is 10 to 400-4/ll.Claims 1 to 2 O ) C) A method for producing a plated metal plate according to any one of item 1. (4) The above-mentioned anodic electrolytic treatment (first treatment): Washing and drying the slightly stretched table board with water, and then applying a resin paint Y Hotaru 11J to form a transparent or translucent coating film.Claim 1
Q) Manufacturing method 1 of plated metal plate as described in any one of claims 1 to 3, (9) Any one of claims 1 to 4, wherein the metal plate is a copper plate or a non-ferrous metal plate. The method for manufacturing a plated metal plate according to item 1. (6) One type of water-soluble Co, Ni or Mo compound is used as a metal and Co and Ni are 3 to 5097.
M, M (for +, 0.01'-3y/It was added 71>f) After the metal plate was air-bent plated in an acidic electrogalvanizing bath containing 0.01'-3y/It as the main component, magnetic-5 ~
Anodic electrolysis treatment (first treatment) at 500 coulombs/dze is performed, and then dichromic acid and/or dichromate is applied at 5 to 1
Electric flux 5-500 coulombs/d♂ in a bath containing 00 fA
A method for producing a colored electrogalvanized metal sheet, characterized by subjecting it to cathodic electrolytic treatment (second treatment). (Force) The acidic electrogalvanizing bath further contains at least one or more of each organic compound of water-soluble or water-dispersible polyacrylate copolymer, dicyandiamide formaldehyde, polyvinyl alcohol, or cationic polyamine in a total amount of 0.1 to A method for producing a plated metal according to claim 6, which is a bath containing lQ f/n. (6) The plated metal plate after the cathodic electrolytic treatment (second treatment) is further coated with silicic acid and Any of claims 6 to 7, wherein the aqueous solution containing silicate and/or chromic acid and/or chromate is applied so that the amount of silicon deposited after drying is 10 to 400 apAd. The method for producing a plated metal plate according to item 1. ■ A construction patent for producing a transparent or translucent coating film by washing and drying the metal plate after the cathodic electrolytic treatment (second treatment) and then applying a resin paint. A method for manufacturing a plated metal plate according to any one of claims 6 to 8.Claims 6 to 9, wherein the metal plate is a steel plate or various non-ferrous metal plates. A method for producing a plated metal plate as described in any one of the above items for burial mounds.