JPS62158898A - Manufacture of colored stainless steel stock - Google Patents

Manufacture of colored stainless steel stock

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Publication number
JPS62158898A
JPS62158898A JP29923985A JP29923985A JPS62158898A JP S62158898 A JPS62158898 A JP S62158898A JP 29923985 A JP29923985 A JP 29923985A JP 29923985 A JP29923985 A JP 29923985A JP S62158898 A JPS62158898 A JP S62158898A
Authority
JP
Japan
Prior art keywords
stainless steel
electrolysis
colored
current
current electrolysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP29923985A
Other languages
Japanese (ja)
Other versions
JPH0533320B2 (en
Inventor
Yuji Sone
雄二 曽根
Kayoko Wada
和田　佳代子
Satoru Narutani
成谷　哲
Shigeharu Suzuki
重治 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
Original Assignee
Kawasaki Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kawasaki Steel Corp filed Critical Kawasaki Steel Corp
Priority to JP29923985A priority Critical patent/JPS62158898A/en
Publication of JPS62158898A publication Critical patent/JPS62158898A/en
Publication of JPH0533320B2 publication Critical patent/JPH0533320B2/ja
Granted legal-status Critical Current

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  • Chemical Treatment Of Metals (AREA)

Abstract

PURPOSE:To manufacture the titled stock having colored layer of various color tones and superior resistances for wear and corrosion, by electrolyticaly treating stainless steel stock for construction in electrolyte having a specified compsn. while combining AC current and pulse current electrolysises. CONSTITUTION:Stainless steel stock for construction is electrolytically treated in various electrolytes to improve resistances for wear and corrosion and to form colored layer having various color tones. As electrolyte, aq. soln. contg. hexavalent Cr compd. and sulfuric acid, liquid obtd. by adding permanganate to aq. sulfuric acid, aq. soln. contg. hydroxide of alkali metal or alkali earth metal, or that further incorporated with MnO2, aq. soln. contg. hexavalent Mo compd. and Cr compd. and sulfulic acid, aq. soln. contg. pentavalent V compd. and sulfuric acid, are used. As electrolytic treatment, opposed pole of stainless steel is used, and AC electrolytic treatment with respectively speci fied anode, cathode current densities and <=100Hz frequency and the treatment by pulse current of 0.01-0.1ms electricity conduction time per one pulse are combined.

Description

【発明の詳細な説明】 く技術分野〉 本発明は、建材用を主要な用途とする色ムラの少ない耐
摩耗性および耐食性に優れた着色ステンレス鋼材の製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing a colored stainless steel material, which is mainly used as a building material and has little color unevenness and is excellent in wear resistance and corrosion resistance.

く先行技術とその問題点〉 着色ステンレス鋼材の主要な用途は、建材用であること
から、ステンレス鋼の基本的性質としての耐食性の他に
多様な色調が望み通り得られること、色調の統一性、即
ち、色ムラのないこと、耐摩耗性の良いことが求められ
る。Prior art and its problems〉 The main use of colored stainless steel materials is for building materials, so in addition to corrosion resistance, which is a basic property of stainless steel, it is also important to be able to obtain various color tones as desired, and to maintain uniformity of color tone. That is, it is required to have no color unevenness and good abrasion resistance.

このような要求に対して以下のような従来技術がある。The following conventional techniques exist to meet such requirements.

１）ステンレス鋼材に多彩な色調を付与する方法として
従来より主に硫酸＋クロム酸の混合液を用いたいわゆる
ＩＮｃＯ法か知られている（特開昭５２−３２６２１．
特公昭５２−２５８１７．特公昭５３−３１８１７）。1) The so-called INcO method, which mainly uses a mixed solution of sulfuric acid and chromic acid, has been known as a method for imparting various color tones to stainless steel materials (Japanese Patent Laid-Open No. 52-32621.
Special Publication Showa 52-25817. Special Publication No. 53-31817).

この方法は「着色」工程と「硬膜」工程の２工程からな
るもので各々独立の溶液組成・温度・処理条件で当該工
程を行うものて、製品としてはバッチ式で生産した単板
が主なものである。This method consists of two steps: a "coloring" step and a "hardening" step, each of which is performed using independent solution composition, temperature, and processing conditions.The main product is veneer produced in batches. It is something.

２）ところが、クロム酸と硫酸を含む水溶液中にステン
レス鋼を浸禎すると、表面にクロム酸化物からなる多孔
性の着色皮膜を生成する。しかし、この皮膜は多孔性ゆ
え摩耗性に弱い。従って、これを克服″１−るため着色
皮膜を硬化する方法とじて特公昭５３−３１８１７号、
特公昭５６−２４０４ｂ号に開示されているように、ク
ロム酸と着色液に比し、はるかに低濃度の硫酸とを含む
水溶液中で前記の方法で着色したステンレス鋼板を陰極
として電解を行い、表面に金属クロムを電析することに
より硬化する方法が知られている。2) However, when stainless steel is immersed in an aqueous solution containing chromic acid and sulfuric acid, a porous colored film made of chromium oxide is formed on the surface. However, this film is susceptible to abrasion due to its porous nature. Therefore, in order to overcome this problem, a method for curing the colored film is disclosed in Japanese Patent Publication No. 53-31817.
As disclosed in Japanese Patent Publication No. 56-2404b, electrolysis is carried out in an aqueous solution containing chromic acid and sulfuric acid at a much lower concentration than the coloring liquid, using a stainless steel plate colored by the above method as a cathode. A method of hardening by electrodepositing metallic chromium on the surface is known.

このｒＮＧＯ法は、「着色」工程と「硬膜」工程の２工
程から成るもので、各々独立の溶液組成・温度・処理条
件で、当該工程を行うものであり、主としてバッチ方式
で単板の着色ステンレス鋼材の製造に用いられている。This rNGO method consists of two steps: a "coloring" step and a "hardening" step. Each step is performed using independent solution composition, temperature, and treatment conditions, and is mainly done in a batch method. Used in the production of colored stainless steel materials.

着色ステンレス鋼材を安価に提供するには、工程の省略
化と単板処理に依らない連続ライン化が必要となる。即
ち、「着色」、「硬膜」という２工程では、この間に水
洗・乾燥という操作をしないと連続ライン化できない。In order to provide colored stainless steel materials at low cost, it is necessary to simplify the process and create a continuous line that does not rely on veneer processing. That is, the two steps of "coloring" and "hardening" cannot be made into a continuous line unless washing with water and drying are performed in between.

また単板処理の場合でも「着色液」、「硬膜液」の２液
を必要とする。ここから、「着色」、「硬膜」をｌ液１
Ｆ程で行い得れば、工程が簡略化でき、連続ラインでの
着色ステンレス鋼の製造が工業上可能となる。Furthermore, even in the case of veneer processing, two liquids are required: a "coloring solution" and a "hardening solution." From here, add 1 liquid of “coloring” and “dura”.
If it can be carried out in about F, the process can be simplified and colored stainless steel can be produced industrially in a continuous line.

さらにＩ　Ｎ（：０法等の「着色」、「硬膜」という２
工程による方法では、前述のように連続化のためにはこ
の間で水洗・乾燥という操作が不可欠であり、［硬膜」
工程において着色時の色調が変化するため、その前の「
着色」工程において最終的な決った色調を得るためには
、予めこの色調変化を見込んだ処理を行うという煩雑な
操作を要すること及び「着色」処理において主に利用さ
れている浸漬法では、被着色物の端面において色ムラか
不可避的に生ずるという問題がある。In addition, there are two methods called ``coloring'' and ``dural mater'' such as IN(:0 method).
In the process-based method, as mentioned above, in order to achieve continuity, operations such as washing with water and drying are essential during this period.
Because the color tone changes during the coloring process, the
In order to obtain a final fixed color tone in the "coloring" process, it is necessary to carry out a process that takes into account this color change in advance, which is a complicated operation, and the dipping method mainly used in the "coloring" process There is a problem in that color unevenness inevitably occurs on the end surface of the colored object.

３）また、このような硫酸＋クロム酸を用いると、公害
的見地から溶液の処理に経費がかかることから、６価ク
ロムを用いない着色液として硫酸十過マンガン酸塩に浸
漬着色する方法が知られている（特公昭５ｌ−４０８６
１）。これは硫酸水溶液に過マンガン酸塩を添加し酸素
ガスの発生が止むまで反応させた溶液にステンレス鋼を
９０〜１１０℃の温度範囲で浸漬し、ブロンズ、黒褐色
、黒色等の着色皮膜を形成せしめる方法である。3) Also, if such sulfuric acid + chromic acid is used, processing of the solution is expensive from a pollution standpoint, so a method of immersing it in sulfuric acid tenpermanganate as a coloring solution that does not use hexavalent chromium is recommended. Known (Special Publication Showa 5l-4086
1). This involves adding permanganate to an aqueous sulfuric acid solution and allowing the reaction to occur until the generation of oxygen gas stops, then immersing stainless steel in a temperature range of 90 to 110°C to form a colored film of bronze, dark brown, black, etc. It's a method.

この溶液以外にも様々な着色液が開発されており、その
中の１つとして水酸化ナトリウム（またはカリウム）十
過マンガン酸カリウム（またはナトリウム）の熱溶液に
自然浸漬着色する方法が知られている（特公昭５４−３
０９７０）。In addition to this solution, various coloring solutions have been developed, one of which is a method of natural immersion in a hot solution of sodium (or potassium) hydroxide and potassium (or sodium) tenpermanganate. There is (Special Public Service 1976-3)
0970).

硫酸と過マンガン酸塩の混合水溶液で浸漬着色する場合
、９０〜１１０℃という非常に高温で行うため、溶液の
蒸発による濃度変化が大きいので溶液の管理が難しい。When coloring by dipping with a mixed aqueous solution of sulfuric acid and permanganate, it is carried out at a very high temperature of 90 to 110° C., so it is difficult to control the solution because the concentration changes greatly due to evaporation of the solution.

また蒸気がでるので作業者の安全衛生上問題があり、大
規模な排気処理設備を施す必要が生じ、これがコストを
上昇させる要因となる。In addition, steam is emitted, which poses health and safety problems for workers, and requires large-scale exhaust treatment equipment, which increases costs.

また、水酸化ナトリウムと過マンガン酸カリウム（また
はナトリウム）により着色酸化させる方法は、過マンガ
ン酸カリウム（またはナトリウム）だけでは酸化力が弱
いため、酸化促進剤として水酸化ナトリウム（またはカ
リウム）を用いたもので、液温９０〜１３０℃、１０〜
２０分浸漬で黒染される。過マンガン酸カリウム（また
はナトリウム）と水酸化ナトリウム（またはカリウム）
で自然浸漬着色する場合、９０〜１３０℃と非常に高温
で行うため溶液の濃度変化が激しく溶液管理が難しい。In addition, the method of coloring and oxidizing with sodium hydroxide and potassium permanganate (or sodium) uses sodium hydroxide (or potassium) as an oxidation promoter, since potassium permanganate (or sodium) alone has weak oxidizing power. liquid temperature 90~130℃, 10~
It is dyed black by soaking for 20 minutes. Potassium (or sodium) permanganate and sodium (or potassium) hydroxide
When natural immersion coloring is carried out at a very high temperature of 90 to 130°C, the concentration of the solution changes drastically and solution management is difficult.

また高温処理のため色ムラも生じやすいという問題点が
ある。この色ムラになりやすいという欠点は、建材用、
意匠用など全ての用途において致命的なものであり、こ
の点を解決しないと、工業的生産はできない。Another problem is that color unevenness tends to occur due to the high temperature treatment. The disadvantage of this tendency to uneven color is that for building materials,
This is fatal for all uses, including design, and unless this point is resolved, industrial production will not be possible.

４）このため本出願人は、すでに特願昭５９−２６０４
９７号、特願昭５９−２４７５４２号、特願昭６０−２
００８２１号、特願昭６０−２００８２２号、特願昭６
０−２００８２３号、特願昭６０−２００８２４号、特
願昭６０−２００８２５号および特願昭６０−２４４７
８３号等を出願し、クロム酸、過マンガン酸、モリブデ
ン酸、バナジウム酸水溶液等の複数の価数をとる金属等
のイオンを含む着色電解液中で、ステンレス鋼材に交番
′准流電解を施して着色するステンレス鋼材の製造方法
を開示している。4) For this reason, the applicant has already filed a patent application in 1983-2604.
No. 97, Japanese Patent Application No. 59-247542, Japanese Patent Application No. 1987-2
No. 00821, Japanese Patent Application No. 1983-200822, Japanese Patent Application No. 1983
0-200823, Japanese Patent Application No. 60-200824, Japanese Patent Application No. 60-200825, and Japanese Patent Application No. 1987-2447
No. 83, etc., and applied alternating current electrolysis to stainless steel materials in a colored electrolyte containing ions of metals with multiple valences such as chromic acid, permanganic acid, molybdic acid, and vanadate aqueous solution. Discloses a method for producing stainless steel material that is colored using a method of coloring.

これらの方法によれば、ＩｆＬｌ工程で多彩な色調を持
ち、色ムラのない耐摩耗性の改簿された着色ステンレス
鋼材が得られるが、さらに着色皮膜を細粒化することが
できれば、良好な耐摩耗性と耐食性を合わせ持つ着色ス
テンレス鋼材が得られることから、さらにこれらの方法
を改善する必要がある。According to these methods, colored stainless steel materials with various color tones and wear resistance without color unevenness can be obtained in the IfLl process, but if the colored film can be made finer in size, it will be possible to obtain a good quality stainless steel material. There is a need to further improve these methods since colored stainless steel materials can be obtained that are both wear and corrosion resistant.

〈発明の目的〉 本発明は、上述した従来技術の問題点を解決しようとし
てなされたものであり、その目的とするところは、着色
ステンレス鋼材の耐摩耗性及び耐食性を著しく向丘させ
るとともに、このような多彩な色調を持つ着色ステンレ
ス鋼材を１液１工程で製造することができる着色ステン
レス鋼材の製造方法を提供しようとするにある。<Object of the Invention> The present invention was made to solve the problems of the prior art described above, and its purpose is to significantly improve the wear resistance and corrosion resistance of colored stainless steel materials, and to improve the wear resistance and corrosion resistance of colored stainless steel materials. To provide a method for manufacturing a colored stainless steel material, which can produce colored stainless steel materials having various color tones in one liquid and one step.

〈発明の構成〉 化学着色法による酸化皮膜は、電気化学的には着色電解
液中で陽極電解を行うことにより得られる。また、硬１
摸処理は、着色とは逆に陰極電解を施すことにより、多
孔質な酸化皮膜を強固にしている。本発明は、「着色」
　；陽極電解、「硬膜」：陰極電解という基本的認識を
基にして、鋭意研究を重ねた結果、交互に電流方向を変
えて、電解を行う交番電流電解と、１方向の極めて短時
間の通電を断続的に繰返すパルス電流電解を最適に組合
せることにより１液１工程で耐摩耗性と耐食性に優れた
着色ステンレス鋼が製造されることを見い出した。<Structure of the Invention> An oxide film formed by a chemical coloring method can be obtained electrochemically by performing anodic electrolysis in a colored electrolyte. Also, hard 1
In contrast to coloring, the painting process uses cathode electrolysis to strengthen the porous oxide film. The present invention is "coloring"
;Anodic electrolysis, "Dura membrane": Based on the basic understanding of cathodic electrolysis, as a result of extensive research, we found two methods: alternating current electrolysis, which performs electrolysis by alternating the direction of current, and extremely short-time electrolysis in one direction. It has been discovered that colored stainless steel with excellent wear resistance and corrosion resistance can be produced in a one-liquid, one-step process by optimally combining pulsed current electrolysis in which energization is repeated intermittently.

本発明で用いる着色電解液は、硫酸濃度が高いものにつ
いては、従来は着色用のみに用いられてきたものであり
、硬膜処理ができるとは知られていなかった。The colored electrolyte used in the present invention, which has a high sulfuric acid concentration, has conventionally been used only for coloring, and it was not known that it could be used for film hardening.

また、クロム酸過マンガン酸、モリブデン酸、バナジウ
ム酸等を用いて交番電流電解とパルス電流電解を組合わ
せて良好な着色・硬膜処理が可能であるということは、
全く新しい発見である。In addition, the fact that good coloring and hardening treatment is possible by combining alternating current electrolysis and pulsed current electrolysis using chromic acid permanganic acid, molybdic acid, vanadate acid, etc.
This is a completely new discovery.

すなわち、本発明は、複数の価数をとる金属を含むイオ
ンを含有する着色電解液中で、ステンレス鋼材に交番電
流電解とパルス電流電解とを組合せて施して着色するこ
とを特徴とする着色ステンレス鋼材の製造方法を提供す
るものである。That is, the present invention provides colored stainless steel, which is characterized in that stainless steel is colored by applying a combination of alternating current electrolysis and pulsed current electrolysis to a stainless steel material in a colored electrolyte containing ions containing metals with multiple valences. The present invention provides a method for manufacturing steel materials.

ここで電解液およびその電解条件として以下のようにす
るのか好ましい。Here, it is preferable that the electrolytic solution and its electrolytic conditions be as follows.

（＋）前記着色電解液が、６価クロムとして０．５ｍｏ
１／ｆｆｉ以上のクロム化合物と１ｍｏ１７４２以上の
硫酸を含む混合水溶液であり、 前記交番電流電解が、陽極電流密度０．０１〜３、〇へ
／ｄｍ”、陰極電流密度０．０３〜５．ＯＡ／ｄｍ’、
繰返し数１００Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求の範囲第１
項に記載の着色ステンレス鋼材の製造方法、 （２）前記着色電解液が３０〜７５ｗし％硫酸水溶液に
過マンガン酸塩をＭｎ０４−として、０．５〜１５ｗｔ
％添加して反応させた溶液であり、前記交番電流電解が
、陽極電流密度０．０１〜０　、　ＩＡ／ｄゴ、陰極電
流密度０．０１〜０．ＩＡ／ｄゴ、繰り返し数１０Ｈｚ
以下で行われるものであり、前記パルス電流電解が、１
パルスの通電時間が０．０１〜０．１　ｍｓで行われる
ものである特許請求の範囲第１項に記載の着色ステンレ
ス鋼材の製造方法、 （３）前記着色電解液が、１〜１０冑し％の過マンガン
酸塩と３０〜５０ｗし％のアルカリ金属あるいはアルカ
リ土類金属の水酸化物の混合水溶液であり、前記交番電
流電解が、陽極電流密度０．０１〜０．５＾／ｄｍ”、
陰極電流密度０．０１〜０．５Ａ／ｄｍ”、繰返し数１
０Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０、旧〜
０．１　ｍｓで行われるものである特許請求の範囲第１
項に記載の着色ステンレス鋼材の製造方法、 （４）＠記着色電解液か１〜１０ｗｔ％の過マンガン酸
塩と３０〜５０冑Ｌ％のアルカリ金属あるいはアルカリ
土類金属の水酸化物および１〜５ｗｔ％の一酸化マンガ
ンの混合水溶液であり、前記交番電流電解が、陽極電流
密度０．Ｏ１〜０．５Ａ／ｄ♂、陰極電流密度０．旧〜
０−５Ａ／ｄｍ２、繰返し数５Ｈｚ以Ｆで行われるもの
であり、 ｔ１η記パルス電流電解か、１パルスの通電時間が０、
旧〜０．１　ｍｓで行われるものである特許請求の範囲
第１項に記載に着色ステンレス鋼材の製造方法、 （５）前記着色電解液が６価モリブデンとして、０．５
〜２　ｍｏｌ／ＩＬのモリブデン化合物と、１〜５ＩＩ
＋０１／ＩＬの硫酸と、６価クロムとして、０．５〜２
ｍｏｌ／Ｉｌのクロム化合物とを含む混合水溶液であり
、 前記交番電流電解が陽極電流密度０．０１〜０．５Ａ／
ｄｍ”、陰極電流密度０．０１〜０．５Ａ／ｄｍ’、繰
返し数１０ｔｌｚ以上で行われるものであり、 前記パルス電流電解が、■パルスの通電時間が０．０１
〜０．１　ｍｓで行われるものである特許請求の範囲第
１項に記載の着色ステンレス鋼材の製造方法、 （６）＠記着色電解液が、５価バナジウムとして、０．
５〜１．５　ｍｏｌ／ｆｆｉのバナジウム化合物と、５
〜ｌＯｍｏｌ／ｕの硫酸とを含む混合水溶液であり、前
記交番電流電解が、陽極電流密度０．０１〜０．２Ａ／
ｄｍ”、陰極電流密度０．０１〜０．２Ａ／ｄｍ”、繰
返し数１０Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．Ｏ１
〜０．１　ｍＳで行われるものである特許請求の範囲第
１項に記載の着色ステンレス鋼材の製造方法であること
、 また、前記交番電流電解が交番電流電解槽の対極にステ
ンレス鋼材を用いて行われるものである特許請求の範囲
第１項ないし第７項のいずれかに記載の着色ステンレス
鋼材の製造方法であることが良い。(+) The colored electrolyte is 0.5 mo as hexavalent chromium.
It is a mixed aqueous solution containing a chromium compound of 1/ffi or more and sulfuric acid of 1 mo1742 or more, and the alternating current electrolysis has an anode current density of 0.01 to 3,0/dm" and a cathode current density of 0.03 to 5.OA. /dm',
The pulsed current electrolysis is performed at a repetition rate of 100 Hz or less, and the pulse current electrolysis is carried out with the energization time of one pulse being 0.01
Claim 1, which is performed in ~0.1ms
(2) The colored electrolyte is 30 to 75 w, and permanganate is Mn04- in a sulfuric acid aqueous solution, and 0.5 to 15 wt.
% added and reacted, and the alternating current electrolysis is performed at an anodic current density of 0.01 to 0, IA/d, and a cathode current density of 0.01 to 0. IA/d Go, repetition rate 10Hz
The pulsed current electrolysis is carried out as follows:
The method for manufacturing a colored stainless steel material according to claim 1, wherein the pulse current application time is 0.01 to 0.1 ms, (3) the colored electrolyte is 1 to 10 ms long. It is a mixed aqueous solution of 30% to 50% permanganate and 30% to 50% alkali metal or alkaline earth metal hydroxide, and the alternating current electrolysis is performed at an anode current density of 0.01 to 0.5^/dm. ,
Cathode current density 0.01-0.5A/dm", number of repetitions 1
The pulsed current electrolysis is performed at a frequency of 0 Hz or less, and the pulsed current electrolysis is performed when the energization time of one pulse is 0.
Claim 1, which is performed in 0.1 ms
The method for manufacturing a colored stainless steel material as described in (4) @the colored electrolyte or 1 to 10 wt % permanganate, 30 to 50 wt % alkali metal or alkaline earth metal hydroxide, and 1 It is a mixed aqueous solution of ~5wt% manganese monoxide, and the alternating current electrolysis is performed at an anodic current density of 0. O1~0.5A/d♂, cathode current density 0. Old ~
It is carried out at 0-5 A/dm2, repetition rate of 5 Hz or more, and pulse current electrolysis is performed at t1η, or the energization time of one pulse is 0.
A method for manufacturing a colored stainless steel material according to claim 1, wherein the coloring electrolyte is 0.5 ms as hexavalent molybdenum.
-2 mol/IL of molybdenum compound and 1-5II
+01/IL sulfuric acid and 0.5 to 2 as hexavalent chromium
It is a mixed aqueous solution containing a chromium compound of mol/Il, and the alternating current electrolysis has an anode current density of 0.01 to 0.5 A/I.
dm'', a cathode current density of 0.01 to 0.5 A/dm', and a repetition rate of 10 tlz or more;
The method for manufacturing a colored stainless steel material according to claim 1, wherein the colored electrolyte is produced in a time of 0.1 ms as pentavalent vanadium.
5 to 1.5 mol/ffi of a vanadium compound, and 5
It is a mixed aqueous solution containing ~10 mol/u of sulfuric acid, and the alternating current electrolysis is performed at an anode current density of 0.01 to 0.2 A/u.
dm", a cathode current density of 0.01 to 0.2 A/dm", and a repetition rate of 10 Hz or less. O1
The method for manufacturing a colored stainless steel material according to claim 1, wherein the alternating current electrolysis is performed at a speed of ~0.1 mS, and the alternating current electrolysis is performed using a stainless steel material as a counter electrode of an alternating current electrolyzer. The method for manufacturing a colored stainless steel material according to any one of claims 1 to 7 is preferably carried out.

以下に本発明の着色ステンレス鋼材の製造方法を詳細に
説明する。The method for producing a colored stainless steel material of the present invention will be explained in detail below.

ここでいうステンレス鋼材とは、線材、管材、板材、塊
、異形断面材、粉粒体など任意の形状でよいが、以下の
説明は代表的に銅帯について行う。The stainless steel material mentioned here may be in any shape such as a wire rod, a tube material, a plate material, a lump, an irregular cross-section material, or a powder material, but the following description will be made with reference to a copper strip as a representative example.

本発明の交番電流電解とパルス電流電解の組合せによる
着色ステンレス鋼材の製造方法は、第１図に例示すると
ともに後に詳しく説明するように交番電流とパルス電流
電解を組合わせて印加するものである。The method of manufacturing a colored stainless steel material by a combination of alternating current electrolysis and pulsed current electrolysis according to the present invention is as illustrated in FIG. 1 and described in detail later, in which alternating current and pulsed current electrolysis are applied in combination.

交番電流電解は、着色電解液中において、陰極電解によ
り着色、陰極電解により硬膜という原理に基づいて、ス
テンレス鋼材に対する極性を交互に変えることにより着
色・硬膜を同時に行うものである。すなわち、ステンレ
ス鋼材の着色を１液１工程で行うことができるものであ
る。Alternating current electrolysis is based on the principle that coloring occurs through cathodic electrolysis and hardening through cathodic electrolysis in a colored electrolyte, and coloring and hardening are performed simultaneously by alternating the polarity of the stainless steel material. That is, it is possible to color stainless steel materials in one step using one liquid.

第１図において、縦軸は電解電流密度、横軸は電解時間
を示し、１は陽極電解時間、２は陽極電解電流密度、３
は陰極電解時間、４は陰極電解電流密度である。In Figure 1, the vertical axis shows the electrolytic current density, and the horizontal axis shows the electrolytic time, where 1 is the anodic electrolytic time, 2 is the anodic electrolytic current density, and 3 is the anodic electrolytic current density.
is the cathode electrolysis time, and 4 is the cathode electrolysis current density.

本発明では陽・陰極電解の電流密度と電解時間を適宜に
組み合せ、所定の回数着色電解液中で交番電流電解を行
う。In the present invention, alternating current electrolysis is performed in a colored electrolyte a predetermined number of times by appropriately combining the current density and electrolysis time of anode/cathode electrolysis.

本発明では、さらに交番電流電解とパルス電流電解を組
み合わせてステンレス鋼材の着色・硬膜処理を行う。In the present invention, furthermore, alternating current electrolysis and pulsed current electrolysis are combined to color and harden stainless steel materials.

ここで、パルス電流電解とは、第１図に例示するように
、通電時間が例えばミリ秒オーダーで、交番電流電解の
通電時間に比して短く、正のパルス電流５でも負のパル
ス電流６でもよく、通電の次にかならず非通電区間があ
り、この通電−非通電が２以上繰り返される。Here, as illustrated in FIG. 1, pulsed current electrolysis means that the energization time is on the order of milliseconds, which is shorter than the energization time of alternating current electrolysis. However, there is always a non-energized section after energization, and this energization/de-energization is repeated two or more times.

一般的には、パルスは、通電時間と非通電時間との比が
１：１が基本であり、本発明の実施例についても１．１
で行った。Generally, the pulse has a ratio of energized time to non-energized time of 1:1, and the ratio of the energized time to the non-energized time is 1:1.
I went there.

しかし、本発明のパルス電流電解は、必要な場合は１：
１以外の通電時間と非通電時間の比としてもよい。However, the pulsed current electrolysis of the present invention can be performed by:
The ratio of the energized time to the non-energized time may be set to a value other than 1.

これに対し、交番電流電解とは、通電時間が例えば秒オ
ーダーで、＋、−交互に繰り返される。On the other hand, in alternating current electrolysis, the energization time is, for example, on the order of seconds, and is repeated alternately.

１パルスの通電時間７は、用いる着色電解液等によって
も異なるもので、後に詳述する。The energization time 7 for one pulse varies depending on the colored electrolyte used, and will be described in detail later.

次に、交番電流電解とパルス電流電解の組合せ方は、交
番電流電解の途中に少なくとも１回または交番電流電解
の後に少なくとも１回パルス電流電解を施す。Next, regarding the combination of alternating current electrolysis and pulsed current electrolysis, pulsed current electrolysis is performed at least once during alternating current electrolysis or at least once after alternating current electrolysis.

このような場合の通電パターンの一＝−例を挙げると、
次の■〜■のようなものがある。To give an example of the energization pattern in such a case,
There are things like the following ■～■.

■交番電流→正のパルス電流→交番電流■交番電流→負
のパルス電流→交番電流■交番電流→正のパルス電流→
負のパルス電流→交番電流 ■交番電流→負のパルス電流 ■交番電流→正のパルス電流→交番電流→負のパルス電
流 ■交番電流→正のパルス電流→負のパルス電流■上記■
〜■のうちの１つを複数回繰り返す■上記■〜■の２以
上を組み合せる また、これらの組合せ電解において、電解初期には、正
の電流密度および／または通電時間を大とし、電解後期
には、負の電流密度および／または通電時間を大とする
傾向にするのか良い。■Alternating current → Positive pulse current → Alternating current ■Alternating current → Negative pulse current → Alternating current ■Alternating current → Positive pulse current →
Negative pulse current → Alternating current ■ Alternating current → Negative pulse current ■ Alternating current → Positive pulse current → Alternating current → Negative pulse current ■ Alternating current → Positive pulse current → Negative pulse current ■ Above ■
Repeat one of ~ ■ multiple times ■ Combining two or more of the above ■ ~ ■ In addition, in these combination electrolysis, the positive current density and/or energization time are increased in the early stage of electrolysis, and in the late stage of electrolysis, For this purpose, it is better to tend to increase the negative current density and/or current application time.

ただし、このような通電パターンにおいては、最後の硬
１漠処理がなされるように、最後に印加する電流は交番
電流の負電流側か負のパルス電流であるのが好ましい。However, in such an energization pattern, it is preferable that the last applied current be the negative current side of the alternating current or a negative pulse current so that the final hardening process can be performed.

なお、正および負の電流の強さ、回数、通電時間等は適
宜選定すればよい。Note that the strength, number of times, energization time, etc. of the positive and negative currents may be appropriately selected.

このような正・負のパルス電流電解によりステンレス鋼
材に着色・硬１１５１がなされる原理は、必ずしも明確
ではないが、正のパルス電流を与えるとスピネル結晶の
成長を促しステンレス表面に皮膜を形成し、負のパルス
電流を与えると成長により柱状構造となったスピネル結
晶の封孔作用を果たし皮膜を均一化して硬膜するものと
考えられる。The principle behind the coloring and hardening of stainless steel materials by positive and negative pulsed current electrolysis is not necessarily clear, but applying a positive pulsed current promotes the growth of spinel crystals and forms a film on the stainless steel surface. It is thought that when a negative pulse current is applied, a pore-sealing effect is performed on the spinel crystal, which has grown into a columnar structure, and the film becomes uniform and hardened.

次に、着色電解液としては、複数の価数をとる金属を含
むイオンを含有するものを用いる。このようなイオンに
は、イ列えばＣｒ”、　ＭｎＯ４、Ｍｎ０４　”、ｖ５
＋（Ｍｖ０３（メタバナジウム酸塩）、Ｍ４Ｖ２０７（
ピロバナジウム酸塩）、Ｍ３ＶＯ４（オルトバナジウム
酸塩＞（Ｍは１価陽イオン）〕等を含む水溶性イオンを
挙げることができる。Next, as the colored electrolyte, one containing ions containing metals having a plurality of valences is used. Such ions include Cr'', MnO4, Mn04'', v5
+(Mv03 (metavanadate), M4V207(
Examples include water-soluble ions including M3VO4 (orthovanadate), M3VO4 (orthovanadate>(M is a monovalent cation)), and the like.

このように、本発明では着色電解液の組成および交番電
流電解の電解条件およびパルス電流電解の電解条件（陽
極電流密度、陰極電流密度、繰り返し数パルス数等）等
を種々選択することができる。As described above, in the present invention, the composition of the colored electrolyte, the electrolytic conditions of alternating current electrolysis, the electrolytic conditions of pulsed current electrolysis (anode current density, cathode current density, number of repetition pulses, etc.), etc. can be variously selected.

以下、着色電解液の組成および電解条件等の好適例につ
いて説明する。Preferred examples of the composition of the colored electrolytic solution, electrolytic conditions, etc. will be described below.

ただし、本発明は下記の例示に限定されるものではない
。However, the present invention is not limited to the following examples.

〔１〕６価クロムとして、０．５　ｍｏｌ／ｆｆｉ以上
のクロム化合物と１　［１Ｉｏｌ／ｊｌの硫酸を含む混
合溶液中において、陽極電流密度０．０１〜３．ＯＡ／
ｄｍ２、陰極電流密度０．０３〜５．ＯＡ／ｄｍ２、繰
返し数１００Ｈｚ以下の交番電流電解と、１パルスの通
電時間が０．Ｏ１〜Ｏ，１ｍｓであるパルス電流電解と
を行う。[1] As hexavalent chromium, in a mixed solution containing 0.5 mol/ffi or more of a chromium compound and 1[1 Iol/jl of sulfuric acid, an anode current density of 0.01 to 3. OA/
dm2, cathode current density 0.03-5. OA/dm2, alternating current electrolysis with a repetition rate of 100 Hz or less, and 1 pulse energization time of 0. Pulse current electrolysis is performed for O1 to O, 1 ms.

６価クロムとして用いるクロム酸塩には無水クロム酸、
重クロム酸ナトリウム、重クロム酸カリウム等の水′溶
性化合物を代表的に挙げることができる。Chromate used as hexavalent chromium includes chromic anhydride,
Representative examples include water-soluble compounds such as sodium dichromate and potassium dichromate.

着色電解液の組成を上記に限定した理由を説明する。The reason why the composition of the colored electrolyte was limited to the above will be explained.

６価クロムが０．５　ｍｏｌ／Ｉ１．未満では酸化能力
が低く、着色に長時間を要すること、および十分な耐摩
耗性をもたせられないからである。また硫酸が１　ｍｏ
ｌ／ＩＬ未満では着色処理で長時間を要するからである
。Hexavalent chromium is 0.5 mol/I1. This is because if it is less than that, the oxidizing ability is low, it takes a long time for coloring, and sufficient abrasion resistance cannot be provided. Also, 1 mo of sulfuric acid
This is because if it is less than 1/IL, the coloring process will take a long time.

交番電流電解の条件を上記に限定した理由を説明する。The reason why the conditions for alternating current electrolysis are limited to the above will be explained.

（１）陽極電解電流密度 陽極電解電流密度が０　、０１　Ａ／ｄは未満では全く
着色しない。また、３．０Ａ／ｄｍ”超では干渉色を有
する均一な皮膜が得られな いので、陽極電解電流密度は０．０１〜３、〇へ／ｄば
の範囲とする。(1) Anodic electrolysis current density If the anodic electrolysis current density is less than 0.01 A/d, no coloring occurs at all. Further, since a uniform film having interference color cannot be obtained at a current density exceeding 3.0 A/d'', the anodic electrolytic current density is set in the range of 0.01 to 3.0/dB.

（２）陰極電解電流密度 陰極電解電流密度が０．０３八／ｄｍ”未満では皮膜は
後述の耐摩耳性試験で容易に剥離する。また、５．ＯＡ
／ｄｍ”以上では鋼板表面は、全面全屈光沢になり着色
した鋼板とは云い難いので、陰極電解電流密度は０．０
３〜５．ｆ）Ａ／ｄｍ”の範囲とする。(2) Cathode electrolysis current density If the cathode electrolysis current density is less than 0.038/dm, the film will easily peel off in the abrasion resistance test described below.
/dm" or more, the surface of the steel sheet becomes completely glossy and cannot be called a colored steel sheet, so the cathode electrolytic current density is 0.0.
3-5. f) A/dm” range.

（３）繰り返し数 電解繰り返し数が１００Ｈｚを超えると着色しないので
、１００Ｈｚ以下が適する。(3) Repeating number If the electrolytic repeating number exceeds 100 Hz, coloring will not occur, so a frequency of 100 Hz or less is suitable.

パル叉電流電解条件を以下に説明する。The pulse current electrolysis conditions will be explained below.

パルス電流電解は、上述の鋼板電流電解の中途か最後の
部分に行う。陽極電流密度は０．０１〜：１．ＯＡ／ｄ
ｍ”で０．旧〜０．１＋＋ｓのパルス電流を少なくとも
１０秒から６０秒流すことで、着色皮膜を細粒化でき、
さらに陰極電流密度として０．０３〜５、ＯＡ／ｄｍ２
を０．０１〜０．１ｍｓのパルス電流を陽極の場合と同
様に流すことによって、スピネル型酸化物の奥深くまで
封孔を行うことができ、その結果、良好な耐摩耗性と耐
食性を合わせ持つ着色ステンレス鋼が得られる。このよ
うな範囲をはずれると、着色皮膜は脆く、色調も不均一
になる。Pulse current electrolysis is performed in the middle or at the end of the above-mentioned steel sheet current electrolysis. The anode current density is 0.01 to 1. OA/d
By passing a pulse current of 0.1 to 0.1++ s for at least 10 to 60 seconds at m'', the colored film can be made into fine grains.
Furthermore, the cathode current density is 0.03 to 5, OA/dm2.
By passing a pulse current of 0.01 to 0.1 ms in the same way as in the case of the anode, it is possible to seal deep into the spinel type oxide, and as a result, it has both good wear resistance and corrosion resistance. A colored stainless steel is obtained. Outside this range, the colored film will be brittle and the color tone will be non-uniform.

色調調製法としては、上記の条件を満たすある特定条件
で電解繰り返し数、陽極電流密度、陰極電流密度、電解
時間、１パルス通電時間、パルス数、を選択し、交番電
流電解とパルス電流電解を適切に組合わせることで任意
の干渉色が得られる。As a color tone adjustment method, the number of electrolysis repetitions, anode current density, cathode current density, electrolysis time, 1-pulse energization time, and number of pulses are selected under certain specific conditions that satisfy the above conditions, and alternating current electrolysis and pulsed current electrolysis are performed. Any interference color can be obtained by appropriately combining them.

（２）３０〜７５ｗｔ％硫酸水溶液に過マンガン酸塩を
Ｍｎ０４−として０．５〜１５ｗｔ％添加して反応させ
た後、好ましくは温度範囲を４０〜１００℃とした溶液
中でステンレス鋼材に陽極電流密度０．０１〜Ｏ，ｌ八
／ｄへｎ’、陰極電流密度０．０１〜Ｏ，ｌ八／ｄへｎ
’、繰り返し数１０Ｈｚ以下の交番電流電解と、１パル
スの通電時間が０．Ｏ１〜０．１　ｍｓであるパルス電
流電解とを行う。この場合には上記（１）のように、着
色電解液にクロム酸（６価クロム）を用いないため、公
害防止という見地から、廃液処理が容易で、経費かかか
らないという利点がある。(2) After adding 0.5 to 15 wt % of permanganate as Mn04- to a 30 to 75 wt % sulfuric acid aqueous solution and reacting, the anode is applied to stainless steel material in the solution preferably at a temperature range of 40 to 100°C. Current density 0.01~O, n' to l8/d, cathode current density 0.01~O, n' to l8/d
', alternating current electrolysis with a repetition rate of 10 Hz or less, and 1 pulse energization time of 0. Pulse current electrolysis is performed for 01 to 0.1 ms. In this case, as described in (1) above, since chromic acid (hexavalent chromium) is not used in the colored electrolyte, there are advantages in that waste liquid treatment is easy and inexpensive from the standpoint of pollution prevention.

着色電解液の組成を上記に限定した理由を説明する。The reason why the composition of the colored electrolyte was limited to the above will be explained.

（１）硫酸 ３０重量％未満では十分な着色効果が 得られず、７５重量％を超えると着色効果は得られるが
反応が速すぎるので抑制が困難となる。したがって、硫
酸の濃度は３０〜７５重量％の範囲とする。(1) If the amount of sulfuric acid is less than 30% by weight, a sufficient coloring effect cannot be obtained, and if it exceeds 75% by weight, a coloring effect can be obtained, but the reaction is too fast, making it difficult to suppress the reaction. Therefore, the concentration of sulfuric acid is in the range of 30 to 75% by weight.

（２）過マンガン酸塩 硫酸溶液に対する過マンガン酸塩の添 加量はＭｎ０４−として０．５重量％未満では着色力が
弱く、溶液の寿命も短い。また１５重量％を超えると着
色力が飽和してしまう。したがって、過マンガン酸塩は
Ｍｎ０４−として０．５〜１５重蛍％の範囲とする。(2) If the amount of permanganate added to the permanganate sulfuric acid solution is less than 0.5% by weight as Mn04-, the coloring power will be weak and the life of the solution will be short. Moreover, if it exceeds 15% by weight, the coloring power will be saturated. Therefore, the permanganate should be in the range of 0.5 to 15 percent Mn04-.

なお、過マンガン酸塩としては、カリウム、ナトリウム
、リチウム、ルビジウ ム、銀、マグネシウム等の過マンガン酸塩を用いること
ができる。Note that as the permanganate, permanganates such as potassium, sodium, lithium, rubidium, silver, and magnesium can be used.

（３）温度 ４０℃未満では反応性が乏しくほとん ど着色せず、１００℃を超えると着色ムラを生じやすく
、蒸気が多く生じ、適さない。したがって、電解液の温
度は４０〜１００℃の範囲とするのがよい。(3) If the temperature is less than 40°C, the reactivity is poor and hardly any coloring occurs, and if it exceeds 100°C, uneven coloring tends to occur and a lot of steam is generated, making it unsuitable. Therefore, the temperature of the electrolytic solution is preferably in the range of 40 to 100°C.

交番電流電解およびパルス電流電解の条件を上記に限定
した理由を説明する。The reason why the conditions for alternating current electrolysis and pulsed current electrolysis are limited to the above will be explained.

（１）陽極電流密度 ０．０１Ａ／ｄｍ’未満では着色せず、０．１へ／ｄｍ
２を超えると色ムラのない均一な皮膜が得られないので
、陽極電流密度は０゜Ｏ１〜０．１八／ｄｍ”の範囲と
する。(1) No coloring occurs when the anode current density is less than 0.01 A/dm', and it decreases to 0.1/dm
If it exceeds 2, a uniform coating without color unevenness cannot be obtained, so the anode current density is set in the range of 0°O1 to 0.18/dm''.

（２）陰極電流密度 ０、ＯＩＡ／ｄｍ２未満では皮膜が非常にもろく、Ｏ，
ｌへ／ｄｍ’を超えると着色皮膜が得られないので、陰
極電流密度は０．Ｏ１〜０．１八／ｄｍ’の範囲とする
。(2) At cathode current density of 0 and less than OIA/dm2, the film is very brittle;
If it exceeds 1/dm', a colored film cannot be obtained, so the cathode current density is 0. The range is O1 to 0.18/dm'.

（３）　ａり返し数 １０１１７、を超えると着色しないので、１０ｔｌｚ以
下とする。(3) If the number of a repeats exceeds 10117, no coloring will occur, so the number should be 10 tlz or less.

（４）パルス電流電解 鋼板電流電解の途中か最後の部分に行 う。(4) Pulsed current electrolysis Go to the middle or last part of steel plate current electrolysis. cormorant.

陽極電流密度０．０１〜０．１　　へ／ｄゴで、ｌパル
スの通電時間が０．０１〜０．１　ｍｓの正のパルス電
流を、少なくとも１０〜６０秒流すと、着色皮膜の細粒
化の効果があ る。When a positive pulse current with an anode current density of 0.01 to 0.1 to/d and a pulse duration of 0.01 to 0.1 ms is applied for at least 10 to 60 seconds, the fine particles of the colored film are It has the effect of

好ましくは、前述の正のパルス電流′屯解の後に、ある
いは交番電流電解を間に挾んで、さらに陰極電流０．０
１〜０．１八／ｄｍ”で、０．０Ｉ〜Ｏ，ｌ　ｍｓの負
のパルス電流を１０〜６０秒流すと、柱状酸化物の奥深
くまで封孔する効果があり好ましい 。Preferably, after the above-mentioned positive pulse current electrolysis or with alternating current electrolysis in between, a cathode current of 0.0
It is preferable to flow a negative pulse current of 1 to 0.18/dm'' and 0.0 I to 0,1 ms for 10 to 60 seconds, since this has the effect of sealing deep into the columnar oxide.

上記範囲外では着色皮膜が脆く色調も 不均一になるからである。Outside the above range, the colored film will be brittle and the color tone will change. This is because it becomes uneven.

以上の条件で鋼板電流電解とパルス電流電解を組合わせ
て行うことによって着色を行うと、ブロンズ、黒褐色、
金色等の着色ステンレス鋼が得られる。When coloring a steel sheet by a combination of current electrolysis and pulsed current electrolysis under the above conditions, bronze, blackish brown,
A colored stainless steel such as gold is obtained.

（３）ａ、ステンレス鋼材を１〜１０ｗｔ％の過マンガ
ン酸塩と３０〜５０ｗｔ％のアルカリ金属あるいはアル
カリ土類金属の水 酸化物の混合水溶液中で好ましくは４ ０〜９０℃の温度範囲内で、陽極電流 密度０．０１〜０．５Ａ／ｄｍ’、陰極電流密度０．０
１〜０．５Ａ／ｄｍ’、繰り返し数ｌ叶２以下で交番電
流電解と、１パルスの通電時間が ０．０１〜３．０Ａ／ｄｍ２．１　ｍｓであるパルス電
流電解とを行う。(3) a. Stainless steel material is heated in a mixed aqueous solution of 1 to 10 wt% permanganate and 30 to 50 wt% alkali metal or alkaline earth metal hydroxide, preferably within a temperature range of 40 to 90°C. , anode current density 0.01-0.5A/dm', cathode current density 0.0
Alternating current electrolysis is performed at 1 to 0.5 A/dm' with a repetition rate of 2 or less, and pulsed current electrolysis is performed in which the energization time of one pulse is 0.01 to 3.0 A/dm and 2.1 ms.

ｂ、ステンレス鋼材を１〜１０Ｗし％の過マンガン酸塩
、３０〜５０冑Ｌ％のアルカリ金属あるいはアルカリ土
類金属の水 酸化物および１〜５ｗｔ％の二酸化マンガンの混合水溶
液中で、好ましくは ４０〜９０℃の温度範囲内で陽極電流 密度０．０１〜０．５Ａ／ｄｍ２、陰極電流密度０．０
１〜０．５八／ｄｄ、繰り返し数５Ｈｚ以下で交番電流
電解と、１パルスの通電時間 が０．０１〜３．０Ａ／ｄｍ２．１　ｍｓであるパルス
電流電解とを行う。b. Preferably, the stainless steel material is heated at 1 to 10 W in a mixed aqueous solution of 1 to 10% permanganate, 30 to 50 L% of alkali metal or alkaline earth metal hydroxide, and 1 to 5 wt% of manganese dioxide. Anode current density 0.01-0.5A/dm2, cathode current density 0.0 within the temperature range of 40-90℃
Alternating current electrolysis is performed at a rate of 1 to 0.58/dd and a repetition rate of 5 Hz or less, and pulsed current electrolysis is performed in which the energization time of one pulse is 0.01 to 3.0 A/dm2.1 ms.

自然浸漬着色の場合には、浸漬液の液温が約９０〜１３
０℃と高温であるため、色ムラが生じるとともに液の濃
度変化か激しく、溶液管理か難しいが、上記ａ、ｂの場
合では、こわらの欠点か改善される。In the case of natural immersion coloring, the temperature of the immersion liquid is approximately 90-13
Since the temperature is as high as 0° C., color unevenness occurs and the concentration of the solution changes drastically, making it difficult to manage the solution, but in cases a and b above, the drawback of stiffness can be improved.

過マンガン酸塩は、カリウム、ナトリウム塩、カルシウ
ム塩などが好適であり、またアルカリ金属あるいはアル
カリ土類金属の水酸化物は、カリウム、ナトリウム、カ
ルシウムなどの水酸化物が好適である。The permanganate is preferably a potassium salt, a sodium salt, a calcium salt, or the like, and the alkali metal or alkaline earth metal hydroxide is preferably a hydroxide of potassium, sodium, calcium, or the like.

（１）溶液組成 上記着色電解処理液の好適な組成範囲 は次の通りである。(1) Solution composition Suitable composition range of the above colored electrolytic treatment solution is as follows.

過マンガン酸塩（ａおよびｂ） １〜１０ｗｊ％ アルカリまたはアルカリ土類金属の水 酸化物（ａおよびｂ） ３０〜５０ｗｔ％ 二酸化マンガン（ｂ）１〜５ｗｔ％ 水（ａおよびｂ）　残部 このように限定する理由は以下の通り である。Permanganate (a and b) 1~10wj% Alkaline or alkaline earth metal water Oxides (a and b) 30-50wt% Manganese dioxide (b) 1-5wt% Water (a and b) balance The reason for this limitation is as follows. It is.

過マンガン酸塩は１ｗｔ、％未満では酸化力が不足し着
色せず、また１０ｗｔ％を超えても効果があがらないの
で、１〜ｌＯｗｔ％が適当である。If the permanganate is less than 1 wt%, the oxidizing power will be insufficient and no coloring will occur, and if it exceeds 10 wt%, the effect will not be improved, so 1 to 1 wt% is appropriate.

二酸化マンガンも同じ理由で１〜５ Ｗ［％が適当である。Manganese dioxide is also 1-5 for the same reason. W [% is appropriate.

アルカリまたはアルカリ土類金属の水 酸化物は３０ｗｔ％未満では酸化促進剤としての（ｌ＃
ｌきが悪く、５０ｗｔ％を超すと色がマダラになりやす
くなるので、３０〜５０ｗし％が適当である。Alkali or alkaline earth metal hydroxides are less than 30 wt% (l#) as oxidation promoters.
If it exceeds 50wt%, the color tends to become uneven, so 30 to 50wt% is appropriate.

（２）溶液温度 処理液の温度は４０℃未満だと反応性 か低く着色に長時間を要し、９０℃を超すと蒸発の問題
や、色ムラかでるので ４０〜９０℃とするのが好ましい。(2) Solution temperature If the temperature of the treatment solution is less than 40°C, the reactivity will be low and it will take a long time to color. If it exceeds 90°C, there will be problems with evaporation and uneven coloring, so it is preferable to keep the temperature between 40 and 90°C. .

（わ電解条件 交番電流電解の条件は、好適には陽極 電流密度が、０．０１〜０−５Ａ／ｄｍ”、陰極電流密
度が０．０１〜０．５Ａ／ｄｍ”で交互に電解を行わせ
る。陽極電流密度が０．ＯＩＡ／ｄｍ’未満だと着色せ
ず、０．５Ａ／ｄｍ”を超えると色ムラのない均一な膜
が得られないので、 ０、旧〜０．５Ａ／ｄｍ’が適当である。(Electrolysis conditions) The conditions for alternating current electrolysis are preferably anode current density of 0.01 to 0-5 A/dm and cathode current density of 0.01 to 0.5 A/dm. If the anode current density is less than 0.OIA/dm', no coloring will occur, and if it exceeds 0.5A/dm', a uniform film with no color unevenness will not be obtained. ' is appropriate.

また、陰極電流密度が０．０１Ａ／ｄ雇未満だと皮膜が
もろく、０．５Ａ／ｄｍ’を超すと発色しないので、０
．旧〜０．５Ａ／ｄｍ２か適当である。In addition, if the cathode current density is less than 0.01 A/dm, the film will be brittle, and if it exceeds 0.5 A/dm', no color will develop.
．． Old to 0.5A/dm2 is appropriate.

繰り返し数が〔３〕ａの場合は、１０ Ｈｚを超えると着色し難いので、１０Ｈｚ以下とする。If the number of repetitions is [3]a, 10 If the frequency exceeds Hz, coloring is difficult, so the frequency is set to 10 Hz or less.

〔３〕ｂの場合は、５Ｈｚを超えると着色し難いので、
５１１Ｚ以下とするのがよい。[3] In the case of b, it is difficult to color when the frequency exceeds 5Hz, so
It is preferable to set it to 511Z or less.

（４）パルス電流電解 交番電流電解の途中か最後の部分に行 う。(4) Pulsed current electrolysis Go to the middle or last part of alternating current electrolysis. cormorant.

陽極電流密度０．０１〜０．１　　Ａ／ｄｍ’で、１パ
ルスの通電時間が０．０１〜３．０Ａ／ｄｍ２．１　ｍ
ｓの正のパルス電流を、少なくとも１０〜６０秒流すと
、着色皮膜の細粒 化の効果がある。The anode current density is 0.01 to 0.1 A/dm', and the energization time of one pulse is 0.01 to 3.0 A/dm2.1 m.
Flowing a positive pulse current of s for at least 10 to 60 seconds has the effect of making the colored film finer.

好ましくは、前述の正のパルス電流電 解の後に、あるいは交番電流電解を間 に挾んで、さらに陰極電流０．０１〜０．５Ａ／ｄｍ”
で、０．０１〜０．１　ｍｓの負のパルス電流を１０〜
６０秒流すと、柱状酸化物の奥深くまで封孔するの効果
があり好ましい。Preferably, after the above-mentioned positive pulse current electrolysis or with alternating current electrolysis in between, a cathode current of 0.01 to 0.5 A/dm is further applied.
Then, apply a negative pulse current of 0.01 to 0.1 ms to 10 to
Flowing for 60 seconds is preferable since it has the effect of sealing deep into the columnar oxide.

上記範囲外では着色皮膜は脆く、色調 も不均一になるからである。Outside the above range, the colored film will be brittle and the color will be This is because it also becomes non-uniform.

〔４〕５僅のバナジウムとして０．５〜１．５　ｍｏｌ
／４１の５価のバナジウムと５〜１０ｍｏｌ／ｊＬの硫
酸を含む混合溶液中において、陽極電流密度０．０１〜
３．０Ａ／ｄｍ２．２Ａ／ｄ♂、陰極電流密度０８０１
〜０．２Ａ／ｄｍ２、繰り返し数１０Ｈｚ以下の交番電
流電解と、１パルスの通電時間が０．旧〜０．１　ｍｓ
であるパルス電流電解とを１：ｒ′う。[4] 5 0.5 to 1.5 mol as a small amount of vanadium
In a mixed solution containing pentavalent vanadium of /41 and sulfuric acid of 5 to 10 mol/jL, an anode current density of 0.01 to
3.0A/dm2.2A/d♂, cathode current density 0801
~0.2A/dm2, alternating current electrolysis with a repetition rate of 10Hz or less, and 1 pulse energization time of 0. Old ~0.1 ms
The pulse current electrolysis is 1:r'.

５価バナジウムとして用いる化合物は、バナジウム酸ナ
トリウム等の水溶性化合物が代表的に挙げられる。A typical example of the compound used as pentavalent vanadium is a water-soluble compound such as sodium vanadate.

着色電解液の組成を１記に限定した理由を説明する。The reason why the composition of the colored electrolytic solution is limited to 1 will be explained.

（１）５価のバナジウム（バナジウム酸化合物）５価バ
ナジウムとして０．５　ｍｏｌ／ｕ未満では、酸化能力
が低く、着色に長時間を要することおよび十分な耐摩耗
性をもたせられないこととなり、１．５　ｍｏｌ／４１
を超えると効果が飽和状態となる。(1) Pentavalent vanadium (vanadate compound) If the amount of pentavalent vanadium is less than 0.5 mol/u, the oxidation ability will be low, it will take a long time for coloring, and sufficient wear resistance will not be provided. 1.5 mol/41
When it exceeds , the effect becomes saturated.

（２）硫酸 ０．５　ｍｏｌ／Ｉ１未満では、着色処理で長時間を要
することとなり、１０ｍｏｌ／Ｉｌを超えると均一に着
色せず、硬１漠も十分に行われず、良好な耐摩耗性が得
られなくなる。(2) If the sulfuric acid content is less than 0.5 mol/Il, the coloring process will take a long time, and if it exceeds 10 mol/Il, the coloring will not be uniform and the hardness will not be sufficiently achieved, resulting in poor wear resistance. You won't be able to get it.

交番電流電解の条件を上記に限定した理由を説明する。The reason why the conditions for alternating current electrolysis are limited to the above will be explained.

（＋）陽極電流密度 ０．０ＩＡ／ｄｍ’未満では着色せず、０．２Ａ／ｄｍ
”を超えると色ムラのない均一な皮膜が得られないので
、陽極電流密度は０． ０１〜０．２Ａ／ｄｍ’の範囲とする。(+) No coloring at anode current density of less than 0.0IA/dm', 0.2A/dm'
If it exceeds 100%, a uniform film without color unevenness cannot be obtained, so the anode current density is set in the range of 0.01 to 0.2A/dm'.

（２）陰極電流密度 ０．０１八／ｄｍ’未満では皮１摸が非常にもろく、０
．２八／ｄｍ”を超えると着色皮膜か得られないので、
陰極電流密度は０．旧〜０．２八／ｄばの範囲とする。(2) When the cathode current density is less than 0.018/dm', the skin becomes very brittle;
．． If it exceeds 28/dm", a colored film cannot be obtained, so
The cathode current density is 0. The range is from old to 0.28/dba.

（３）繰り返し数 １０Ｈｚを超えると着色しないので、 １０Ｈｚ以下とする。(3) Number of repetitions If the frequency exceeds 10Hz, it will not be colored, so The frequency shall be 10Hz or less.

（４）パルス電流電解 交番電流電解の途中か最後の部分に行 う。(4) Pulsed current electrolysis Go to the middle or last part of alternating current electrolysis. cormorant.

陽極電流密度０．旧〜０．２　　八／ｄｍ”で、１パル
スの通′１゛「時間が０．０１〜Ｏ，ｌ　ｍｓの正のパ
ルス電流を、少なくとも１０〜６０秒流すと、着色皮膜
の細粒化の効果がある 。Anode current density 0. When a positive pulse current of 0.2 8/dm and 1 pulse duration of 0.01 to 0,1 ms is applied for at least 10 to 60 seconds, the colored film becomes finer. There is an effect.

好ましくは、前述の正のパルス電流 電解の後に、あるいは交番電流電解を 間に挾んで、さらに陰極電流０．０１〜０．２Ａｌｄｄ
で、０．０１〜０．１　ｍｓの負のパルス電流を１０〜
６０秒流すと、柱状酸化物の奥深くまで封孔する効果が
あり好まし い。Preferably, after the above-mentioned positive pulse current electrolysis or with alternating current electrolysis in between, a cathode current of 0.01 to 0.2Aldd is further applied.
Then, apply a negative pulse current of 0.01 to 0.1 ms to 10 to
Flowing for 60 seconds is preferable since it has the effect of sealing deep into the columnar oxide.

上記範囲外では着色皮膜が脆く、色調 も不均一になるからである。Outside the above range, the colored film will be brittle and the color will be This is because it also becomes non-uniform.

（５）６価モリブデンとして、０．５〜２．０ｍｏｌ／
　Ｌのモリブデン化合物、６価クロムとして、０．５〜
２、Ｏｌｏｌ／４のクロム化合物（例えばクロム酸）お
よび１〜５ｍｏｌ／ｕの硫酸を含む混合溶液中において
、陽極電流密度０．０１〜３．０Ａ／ｄｍ２．５Ａ／ｄ
ｍ２、陰極電流密度０、０１〜３．０Ａ／ｄｍ２．５Ａ
／ｄゴ、繰り返し数１０Ｈｚ以下の交番電流電解と、１
パルスの」１１ｉ電時間か０．０１〜０．１　ｍｓであ
るパルス電流電解を行う。(5) As hexavalent molybdenum, 0.5 to 2.0 mol/
Molybdenum compound of L, as hexavalent chromium, 0.5 to
2. In a mixed solution containing Olol/4 chromium compound (e.g. chromic acid) and 1-5 mol/u sulfuric acid, anode current density 0.01-3.0 A/dm2.5 A/d
m2, cathode current density 0, 01-3.0A/dm2.5A
/dgo, alternating current electrolysis with a repetition rate of 10Hz or less, and 1
Pulsed current electrolysis is performed with a pulse duration of 0.01 to 0.1 ms.

６価モリブデンとして用いる化合物はＭｏＯ３、Ｎａ２
　Ｍｏ０４等の水溶性化合物が代表的に挙げられる。Compounds used as hexavalent molybdenum are MoO3, Na2
A typical example is a water-soluble compound such as Mo04.

着色電解液の組成を上記に限定した理由を説明する。The reason why the composition of the colored electrolyte was limited to the above will be explained.

（１）６僅のモリブデン（モリブデン酸化合物）６価モ
リブデンとして、０．５　ｍｏｌ／ｌ未満では、酸化能
力が低く、着色に長時間を要することおよび十分な耐摩
耗性をもたせられないこととなり、２．０　ｍｏｌ／ｆ
ｆｉを超えると効果が飽和状態となる。(1) 6 Molybdenum (molybdic acid compound) If the amount of hexavalent molybdenum is less than 0.5 mol/l, the oxidizing ability will be low, it will take a long time to color, and it will not be able to provide sufficient wear resistance. , 2.0 mol/f
When fi is exceeded, the effect becomes saturated.

（２）６僅のクロム化合物（クロム酸）６価クロムとし
て、　０．５　ｍｏｌ／ｆｆｉ未満では、酸化能力が低
く、着色に長時間を要することおよび十分な耐摩耗性を
もたせられないこととなり、２．０　ｍｏｌ／ｌ１を超
えると効果が飽和状態となる。(2) Chromium compound (chromic acid) If the amount of hexavalent chromium is less than 0.5 mol/ffi, the oxidizing ability will be low, it will take a long time to color, and it will not be able to provide sufficient wear resistance. , 2.0 mol/l1, the effect becomes saturated.

（３）　！酸 １　ｍｏｌ／ＩＬ未満では、着色処理で長時間を要する
こととなり、５ｍｏｌ／ｌを超えると均一に着色せず、
硬膜も十分に行われず、良好な耐摩耗性が得られないこ
ととなる。(3)! If the acid is less than 1 mol/IL, the coloring process will take a long time, and if it exceeds 5 mol/l, the coloring will not be uniform.
Hardening is also not performed sufficiently, and good wear resistance cannot be obtained.

交番電流電解およびパルス電流電解の条件を上記に限定
した理由を説明する。The reason why the conditions for alternating current electrolysis and pulsed current electrolysis are limited to the above will be explained.

（１）陽極電流密度 ０．０１Ａ／ｄｍ’未満では着色せず、０６５Ａ／ｄｒ
＋ｔ’を超えると色ムラのない均一な皮膜が得られない
ので、陽極電流密度は０ 、０１〜３．０Ａ／ｄｍ２．５八／ｄゴの範囲とする。(1) No coloration occurs when the anode current density is less than 0.01A/dm', and 065A/dr
If it exceeds +t', a uniform film without color unevenness cannot be obtained, so the anode current density is set in the range of 0.01 to 3.0 A/dm2.58/d.

（２）陰極電流密度 ０．０１Ａ／ｄｍ”未満では皮膜が非常にもろく、０．
５Ａ／ｄｍ２を超えると着色皮膜が得られないので、陰
極電流密度は０．０１〜３．０Ａ／ｄｍ２．５５Ａ　Ａ
／ｄｍ”の範囲とする。(2) If the cathode current density is less than 0.01 A/dm, the film will be very brittle;
If it exceeds 5A/dm2, a colored film cannot be obtained, so the cathode current density is 0.01 to 3.0A/dm2.55A A
/dm” range.

（３）繰り返し数 １０Ｈｚを超えると着色しないので、 １０１（ｚ以下とする。(3) Number of repetitions If the frequency exceeds 10Hz, it will not be colored, so 101 (shall be less than or equal to z.

（４）パルス電流電解 交番電流電解の途中か最後の部分に行 う。(4) Pulsed current electrolysis Go to the middle or last part of alternating current electrolysis. cormorant.

陽極電流密度０．０１〜３．０Ａ／ｄｍ２．５　　Ａ／
ｄゴで、１パルスの通電時間が０．０１〜３．０Ａ／ｄ
ｍ２．１　ｆｆ１ｓの正のパルス電流を、少なくとも１
０〜６０秒流すと 、着色皮膜の細粒化の効果がある。Anode current density 0.01-3.0A/dm2.5A/
d Go, 1 pulse energizing time is 0.01 to 3.0A/d
m2.1 ff1s positive pulse current at least 1
Flowing for 0 to 60 seconds has the effect of making the colored film finer.

好ましくは、前述の正のパルス電流電 解の後に、あるいは交番電流電解を間 に挾んで、さらに陰極電流Ｏ０旧〜０．５Ａ／ｄｍ”で
、０．０１〜０．１　ｍｓの負のパルス電流を１０〜６
０秒流すと、柱状酸化物の奥深くまで封孔する効果があ
り好ましい 。Preferably, after the above-mentioned positive pulsed current electrolysis or with alternating current electrolysis in between, a negative pulsed current of 0.01 to 0.1 ms is further applied at a cathode current of 0 to 0.5 A/dm. 10 to 6
Flowing for 0 seconds is preferable since it has the effect of sealing deep into the columnar oxide.

上記範囲外では着色皮膜が脆く色調も 不均一になるからである。Outside the above range, the colored film will be brittle and the color tone will change. This is because it becomes uneven.

以上に説明した交番電流電解とパルス電流電解によるス
テンレス鋼材の着色においては、ステンレス鋼帯に対す
る対極９として、通常、安定な金属（例えばＧ　、　Ｐ
Ｌ、　Ｐｂ、　Ｔｉ、　Ｐｂ−５ｎ合金等）が用いられ
る。In coloring stainless steel materials by alternating current electrolysis and pulsed current electrolysis as described above, stable metals (e.g. G, P) are usually used as the counter electrode 9 to the stainless steel strip.
L, Pb, Ti, Pb-5n alloy, etc.) are used.

しかるに、交番電流′１”に解とパルス電流電解法の場
合、対極９においても被着色材と同様に陽極電解と陰極
電解が繰り返され、さらにパルス電流電解が行われると
いう特徴を存するので、同一材料を対極として用いた場
合、対極での交番電流電解を有効に利用でき、生産の効
率向上を図ることか可能となる。However, in the case of pulsed current electrolysis using an alternating current '1'', the counter electrode 9 has the characteristic that anodic electrolysis and cathodic electrolysis are repeated in the same way as the material to be colored, and pulsed current electrolysis is also performed. When the material is used as a counter electrode, alternating current electrolysis at the counter electrode can be effectively used, making it possible to improve production efficiency.

そこで、電解槽の対極９にステンレス鋼材を用いること
が良い。即ち、この対極として用いたステンレス鋼もま
た被着色材と同様の着色ステンレスとなり、かつ、得ら
れた２枚の着色ステンレス鋼板は色調、耐摩耗性等の性
状に差が生じない。Therefore, it is preferable to use stainless steel material for the counter electrode 9 of the electrolytic cell. That is, the stainless steel used as the counter electrode is also colored stainless steel similar to the material to be colored, and the two obtained colored stainless steel plates have no difference in properties such as color tone and abrasion resistance.

なお、当然のことながらステンレス対極を用いる場合に
ついては、着色ステンレス極に対して対極となるステン
レスの電解時期をずらして行う。Note that, as a matter of course, when a stainless steel counter electrode is used, the electrolysis timing of the stainless steel counter electrode is shifted from that of the colored stainless steel electrode.

この方法は、バッチ式にも連続式に適用できる。バッチ
式では２枚の組合せを１セツトとし、これを１セツト以
上セットとして着色処理することができる。連続式では
、２枚以上のステンレス鋼材を対向して流すことにより
これらを同時に着色処理することができる。This method can be applied both batchwise and continuously. In the batch method, two sheets are combined as one set, and one or more sets can be colored. In the continuous method, two or more stainless steel materials can be colored at the same time by flowing them facing each other.

本発明の着色ステンレス鋼材の製造において以下のよう
な前処理を行うことも良い。In producing the colored stainless steel material of the present invention, the following pretreatment may also be performed.

着色ステンレス屑材の製造における前処理として、一般
的には油脂類や接着剤を除去するためアルカリによる乳
脂および酸洗が主として浸漬法により行われている。As a pre-treatment in the production of colored stainless steel scrap materials, milk fat and pickling with an alkali are generally performed mainly by the immersion method in order to remove fats and oils and adhesives.

これらは汚れの除去を主目的にしたもので、表面皮膜の
均一性を目的としたものではない。The main purpose of these is to remove dirt and not to improve the uniformity of the surface film.

そこで表面皮膜を均一にすることと実工程の簡便さとい
うことを念頭に置き、電解酸洗処理で行うという基本的
認識を基に、電気化学的に検討を重ねた結果、硝酸をベ
ースにした溶液中で、まずカソード処理を行い、続いて
アノード処理を行うという連続的な前処理を行い、複数
の価数をとる金属を含むイオンを含有する着色電解液中
で引き続き交番電流電解およびパルス電流電解を組合せ
て着色処理を行えば均一な色調の色ムラの少ない化学着
色ステンレス鋼板が得られる。Therefore, keeping in mind the need to make the surface film uniform and the simplicity of the actual process, based on the basic understanding that electrolytic pickling treatment is used, and after repeated electrochemical studies, we decided to use a nitric acid-based method. Sequential pretreatment in solution, first cathodic and then anodic, followed by alternating current electrolysis and pulsed current electrolysis in a colored electrolyte containing ions containing multivalent metals. If coloring treatment is performed in combination with electrolysis, a chemically colored stainless steel sheet with uniform color tone and less color unevenness can be obtained.

次に電解酸洗の処理溶液および処理条件について説明す
る。なお、以下の説明において、％は全てｗ’Ｌ％を意
味する。Next, the treatment solution and treatment conditions for electrolytic pickling will be explained. In addition, in the following explanation, all % means w'L%.

（＋）電解酸洗溶液 “溶液としては１０〜３０％硝酸＋０．５〜５％りん酸
を含むものを用いるのがよい。硝酸を１０〜３０％とし
たのは。(+) Electrolytic Pickling Solution It is preferable to use a solution containing 10 to 30% nitric acid + 0.5 to 5% phosphoric acid.The nitric acid content is 10 to 30%.

１０％未満では酸化力不足で良好な表面不働態皮膜を形
成し得す、また、３０ ％を超えると効果が飽和するためであ る。This is because if it is less than 10%, a good surface passivation film cannot be formed due to insufficient oxidizing power, and if it exceeds 30%, the effect is saturated.

りん酸を加えると、カソード処理にお いて水素ガスの発生が過大とならず、アノード処理での
表面皮膜が均一になる。When phosphoric acid is added, hydrogen gas is not generated excessively during cathodic treatment, and the surface film during anodizing becomes uniform.

このためには、０．５％以上必要であり、５％を超えて
は効果がなくなるので上限を５％とするのが好ましい。For this purpose, 0.5% or more is required, and if it exceeds 5%, the effect will be lost, so it is preferable to set the upper limit to 5%.

また液温は７０℃を越えると鋼板の肌 荒れが過大となるため７０℃以下とす る。下限は２０℃程度が好ましい。Also, if the liquid temperature exceeds 70℃, the skin of the steel plate will be damaged. Keep it below 70℃ as it will cause excessive roughness. Ru. The lower limit is preferably about 20°C.

（２）電解酸洗のカソード処理条件 カソード処理条件は、十分な水素ガ ス気泡でステンレス鋼表面を清浄にす るためには、０．５＾／ｄｍ″は最低必要で、２．０＾
／ｄ♂を超えると分極が大きく、一部フエライト系では
水素脆化割れが懸念されるので０．５Ａ／ｄｍ”〜２．
ＯＡ／ｄｍ”の範囲が好適である。(2) Cathode treatment conditions for electrolytic pickling The cathode treatment conditions require a minimum of 0.5^/dm'' and 2.0^ to clean the stainless steel surface with sufficient hydrogen gas bubbles.
If it exceeds /d♂, the polarization will be large, and hydrogen embrittlement cracking may occur in some ferrite systems, so 0.5A/dm" to 2.
A range of OA/dm" is suitable.

（３）電解酸洗のアノード処理 アノード処理条件は、カソード処理に より清浄化した表面に均質な不働態皮膜を形成させるた
めに行うものである。このためには、０．ＩＡ／ｄｍ’
以下の低電流密度で行うことが肝要で、これを超えると
主として粒界からＣｒ、Ｆｅが溶出するので表面の荒れ
が超こり、均質性が損われるので０．ＪＡ／ｄｍ’以下
が好適である。(3) Anode treatment of electrolytic pickling The anode treatment conditions are performed in order to form a homogeneous passive film on the surface cleaned by cathode treatment. For this, 0. IA/dm'
It is important to carry out the current density at a low current density below 0.0. JA/dm' or less is preferable.

従来の処理法は、浸漬によるものが主体であることから
、金属−溶液界面で起きる反応速度を制御することは難
しいか、本発明にかかる電解酸洗処理によれば条件のＩ
ＩＪ御は電流密度と時間という因子で行うことができ、
長尺物やコイルの化学着色前処理に適した方法でどのよ
うなステンレス鋼の化学組成や表面仕上りにも対処でき
るものである。Since conventional treatment methods mainly involve immersion, it is difficult to control the reaction rate that occurs at the metal-solution interface.
IJ control can be performed using the factors of current density and time.
This method is suitable for chemical coloring pretreatment of long objects and coils, and can be applied to any chemical composition or surface finish of stainless steel.

〈実施例〉 本発明に係る着色ステンレス鋼板の製造方法を実施例に
つき具体的に説明する。<Example> The method for manufacturing a colored stainless steel sheet according to the present invention will be specifically described with reference to an example.

く本発明法〉 ５ＬＩＳ　３０４　ＢＡ　（光輝焼鈍処理）板（大きさ
１００ｘ　１００ｍｍ）を種々の組成の着色電解液に浸
清し、電解条件を種々変更して交番電流電解およびパル
ス電流電解を計２０分行いステンレス板に着色を行った
。Method of the present invention> 5 LIS 304 BA (bright annealing) plates (size 100 x 100 mm) were immersed in colored electrolytes of various compositions, and electrolytic conditions were varied to perform alternating current electrolysis and pulsed current electrolysis for a total of 20 minutes. Coloring was carried out on a stainless steel plate.

く比較法〉 本発明において一部の条件を欠く方法でステンレス板に
着色を行った。Comparative Method> A stainless steel plate was colored by a method lacking some conditions in the present invention.

第１表〜第６表に、本発明の範囲からはずれる条件には
アンダーラインを付して示した。In Tables 1 to 6, conditions outside the scope of the present invention are underlined.

〈従来法〉 交番電流電解およびパルス電流電解法によらず、従来の
自然浸漬を用いた２液・２工程からなる方法により同様
のステンレス板に着色を行った。<Conventional Method> A similar stainless steel plate was colored using a conventional two-liquid, two-step method using natural immersion, without using alternating current electrolysis or pulsed current electrolysis.

これらについて色調、耐摩耗性および耐食性評価を行っ
た。These were evaluated for color tone, abrasion resistance, and corrosion resistance.

（＋）耐摩耗性試験 試料鋼板を、荷重５００ｇの条件で耐摩耗試験機を用い
て、着色皮膜表面を酸化クロム研磨紙で擦ることにより
耐摩耗性試験を行った。耐摩耗性の評価は、着色皮膜が
完全に除去されるまでの酸化クロム研磨紙による摩耗回
数で行い、この回数が多くなる程耐摩耗性が優れている
と判定した。(+) Abrasion Resistance Test A wear resistance test was conducted on the sample steel plate by rubbing the surface of the colored film with a chromium oxide abrasive paper using an abrasion tester under the condition of a load of 500 g. Abrasion resistance was evaluated based on the number of times of abrasion with chromium oxide abrasive paper until the colored film was completely removed, and it was determined that the greater the number of abrasions, the better the abrasion resistance.

（２）耐食性試験 耐食性の評価は、外装として室外で用いる場合、塩害に
よる煮詰の効果をみるため、孔食電位測定（ＪＩＳ　Ｇ
−０５７７、１９８１の規定による）を行い、孔食電位
値が大なる程、耐食性良好とした。(2) Corrosion resistance test Corrosion resistance is evaluated using pitting potential measurement (JIS G
-0577, 1981), and the larger the pitting potential value, the better the corrosion resistance.

いる。There is.

第１表〜第６表に示す着色電解液を用い、評価結果を第
１表〜第６表に示した。The evaluation results are shown in Tables 1 to 6 using the colored electrolytes shown in Tables 1 to 6.

第１表に示す結果から、従来法および比較法での摩耗回
数は、高々３００回程度であるのに比べて、本発明法の
場合、その摩耗回数は、　６９０〜７２０回という約２
．５倍の値であった。From the results shown in Table 1, the number of wears in the conventional method and the comparative method is about 300 times at most, while in the case of the method of the present invention, the number of wears is about 2, 690 to 720 times.
．． The value was five times higher.

耐食性は、従来法および比較法に比べて、本発明法の場
合孔食電位が＋〇、８５Ｖ、ＳＣＥと高く、良好であっ
た。Corrosion resistance was good in the method of the present invention, with a higher pitting potential of +0.85 V, SCE, than in the conventional method and the comparative method.

第２表に示す結果から、比較法での摩耗回数は、３００
回程度であるのに比べて、本発明法では、５８０〜６５
０回という約２倍以上の値である。From the results shown in Table 2, the number of wear using the comparative method is 300.
In contrast, in the method of the present invention, it is about 580 to 65 times.
This value is approximately twice as high as 0 times.

しかも耐食性も孔食電位が＋０．６５〜十〇、ａＶ。Moreover, the corrosion resistance has a pitting potential of +0.65 to 100, aV.

ＳＣεと高く、良好であった。The SCε was high and good.

第３表〜第６表に示す結果からも同様に本発明の製造方
法による着色ステンレス鋼板は耐摩耗性、耐食性に優れ
ていることがわかる。特に、着色電解液に６価モリブデ
ンを含むもの（第５表）および５価バナジウムを含むも
の（第６表）を用いる製造方法は耐摩耗性、耐食性が非
常に優れて〈発明の効果〉 本発明の交番電流電解とパルス電流電解による着色ステ
ンレス鋼材の製造方法は、ステンレス鋼材を６価クロム
、過マンガン酸塩、６価モリブデン、５価バナジウム等
の複数の価数をとる金属を含むイオンを含有する着色電
解液を用いて、１液・１工程で耐摩耗性と耐食性に優れ
た着色ステンレス鋼材を製造するものであり、連続的に
着色ステンレス鋼材を生産する方法に適用できる。The results shown in Tables 3 to 6 also show that the colored stainless steel sheets manufactured by the manufacturing method of the present invention have excellent wear resistance and corrosion resistance. In particular, the production method using colored electrolytes containing hexavalent molybdenum (Table 5) and pentavalent vanadium (Table 6) has excellent wear resistance and corrosion resistance. The method of producing colored stainless steel material by alternating current electrolysis and pulsed current electrolysis of the invention involves treating stainless steel material with ions containing metals with multiple valences such as hexavalent chromium, permanganate, hexavalent molybdenum, and pentavalent vanadium. The method uses a colored electrolyte to produce colored stainless steel materials with excellent wear resistance and corrosion resistance in one solution and one step, and can be applied to a method for continuously producing colored stainless steel materials.

本発明の方法により製造された着色ステンレス鋼材は多
彩な色調を持ち、耐摩耗性及び耐食性において従来のも
のに比べて著しく向上している。The colored stainless steel materials produced by the method of the present invention have a variety of colors and have significantly improved wear resistance and corrosion resistance compared to conventional materials.

なお対極にステンレス鋼材を用いれば、一度に２個以上
着色でき、２倍以上の作業効率が得られ、また同じ電気
量で２倍の着色材を製造することができる。If a stainless steel material is used for the counter electrode, two or more pieces can be colored at once, the working efficiency can be doubled or more, and twice as much coloring material can be produced with the same amount of electricity.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明の交番電流電解とパルス電流電解による
着色ステンレス鋼材の製造方法の電解条件を示すもので
、交番電流電解とパルス電流電解を模式的に示したグラ
フである。 たて軸は、電解電流密度、横軸は、電解時間である。 符号の説明 °　　１・・・陽極電解時間、２・−陽極電解電流密度
、３・・・陰極電解時間、４・・・陰極電解電流密度、
５・・・正のパルス電流、６・・・負のパルス電流、７
−・１パルスの通電時間FIG. 1 shows the electrolytic conditions of the method for producing a colored stainless steel material by alternating current electrolysis and pulsed current electrolysis according to the present invention, and is a graph schematically showing alternating current electrolysis and pulsed current electrolysis. The vertical axis is the electrolysis current density, and the horizontal axis is the electrolysis time. Explanation of symbols ° 1... Anodic electrolysis time, 2 - Anodic electrolysis current density, 3... Cathodic electrolysis time, 4... Cathodic electrolysis current density,
5... Positive pulse current, 6... Negative pulse current, 7
-・Electrification time of 1 pulse

Claims (8)

【特許請求の範囲】[Claims] （１）複数の価数をとる金属を含むイオンを含有する着
色電解液中で、ステンレス鋼材に交番電流電解とパルス
電流電解とを組合せて施して着色することを特徴とする
着色ステンレス鋼材の製造方法。(1) Production of colored stainless steel material, which is characterized by coloring stainless steel material by applying a combination of alternating current electrolysis and pulsed current electrolysis to the stainless steel material in a colored electrolyte containing ions containing metals with multiple valences. Method. （２）前記着色電解液が、６価クロムとして０．５ｍｏ
ｌ／ｌ以上のクロム化合物と１ｍｏｌ／ｌ以上の硫酸を
含む混合水溶液であり、 前記交番電流電解が、陽極電流密度０．０１〜３．０Ａ
／ｄｍ＾２、陰極電流密度０．０３〜５．０Ａ／ｄｍ＾
２、繰返し数１００Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求の範囲第１
項に記載の着色ステンレス鋼材の製造方法。(2) The colored electrolyte is 0.5 mo as hexavalent chromium.
It is a mixed aqueous solution containing 1/l or more of a chromium compound and 1 mol/l or more of sulfuric acid, and the alternating current electrolysis is performed at an anode current density of 0.01 to 3.0 A.
/dm^2, cathode current density 0.03-5.0A/dm^
2. The pulsed current electrolysis is performed at a repetition rate of 100 Hz or less, and the pulse current electrolysis has a energization time of 0.01 per pulse.
Claim 1, which is performed in ~0.1ms
A method for producing colored stainless steel material as described in . （３）前記着色電解液が３０〜７５ｗｔ％硫酸水溶液に
過マンガン酸塩をＭｎＯ＿４として、０．５〜１５ｗｔ
％添加して反応させた溶液であり、 前記交番電流電解が、陽極電流密度０．０１〜０．１Ａ
／ｄｍ＾２、陰極電流密度０．０１〜０．１Ａ／ｄｍ＾
２、繰り返し数１０Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求の範囲第１
項に記載の着色ステンレス鋼材の製造方法。(3) The colored electrolyte is 0.5 to 15 wt% permanganate as MnO_4 in a 30 to 75 wt% sulfuric acid aqueous solution.
% added and reacted, and the alternating current electrolysis is performed at an anode current density of 0.01 to 0.1 A.
/dm^2, cathode current density 0.01-0.1A/dm^
2. The pulse current electrolysis is performed at a repetition rate of 10 Hz or less, and the pulse current electrolysis is performed with the current application time of one pulse being 0.01
Claim 1, which is performed in ~0.1ms
A method for producing colored stainless steel material as described in . （４）前記着色電解液が、１〜１０ｗｔ％の過マンガン
酸塩と３０〜５０ｗｔ％のアルカリ金属あるいはアルカ
リ土類金属の水酸化物の混合水溶液であり、前記交番電
流電解が、陽極電流密度０．０１〜０．５Ａ／ｄｍ＾２
、陰極電流密度０．０１〜０．５Ａ／ｄｍ＾２、繰返し
数１０Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求の範囲第１
項記載の着色ステンレス鋼材の製造方法。(4) The colored electrolyte is a mixed aqueous solution of 1 to 10 wt% permanganate and 30 to 50 wt% alkali metal or alkaline earth metal hydroxide, and the alternating current electrolysis is performed at an anode current density. 0.01~0.5A/dm^2
, the pulsed current electrolysis is performed at a cathode current density of 0.01 to 0.5 A/dm^2 and a repetition rate of 10 Hz or less, and the pulsed current electrolysis is performed with a current application time of 1 pulse of 0.01
Claim 1, which is performed in ~0.1ms
2. Method for producing colored stainless steel material as described in Section 1. （５）前記着色電解液が１〜１０ｗｔ％の過マンガン酸
塩と３０〜５０ｗｔ％のアルカリ金属あるいはアルカリ
土類金属の水酸化物および１〜５ｗｔ％の二酸化マンガ
ンの混合水溶液であり、前記交番電流電解が、陽極電流
密度０．０１〜０．５Ａ／ｄｍ＾２、陰極電流密度０．
０１〜０．５Ａ／ｄｍ＾２、繰返し数５Ｈｚ以下で行わ
れるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求の範囲第１
項に記載の着色ステンレス鋼材の製造方法。(5) The colored electrolyte is a mixed aqueous solution of 1 to 10 wt% permanganate, 30 to 50 wt% of an alkali metal or alkaline earth metal hydroxide, and 1 to 5 wt% of manganese dioxide; Current electrolysis is performed at an anode current density of 0.01 to 0.5 A/dm^2 and a cathode current density of 0.
01 to 0.5 A/dm^2 and a repetition rate of 5 Hz or less, and the pulsed current electrolysis is performed with the current application time of one pulse being 0.01
Claim 1, which is performed in ~0.1ms
A method for producing colored stainless steel material as described in . （６）前記着色電解液が６価モリブデンとして、０．５
〜２ｍｏｌ／ｌのモリブデン化合物と、１〜５ｍｏｌ／
ｌの硫酸と、６価クロムとして、０．５〜２ｍｏｌ／ｌ
のクロム化合物とを含む混合水溶液であり、前記交番電
流電解が陽極電流密度０．０１〜０．５Ａ／ｄｍ＾２、
陰極電流密度０．０１〜０．５Ａ／ｄｍ＾２、繰返し数
１０Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求の範囲第１
項に記載の着色ステンレス鋼材の製造方法。(6) The colored electrolyte is 0.5 as hexavalent molybdenum.
~2 mol/l molybdenum compound and 1~5 mol/l
l of sulfuric acid and 0.5 to 2 mol/l as hexavalent chromium
is a mixed aqueous solution containing a chromium compound, and the alternating current electrolysis has an anode current density of 0.01 to 0.5 A/dm^2,
The pulsed current electrolysis is carried out at a cathode current density of 0.01 to 0.5 A/dm^2 and a repetition rate of 10 Hz or less, and the pulsed current electrolysis is performed with a current conduction time of 1 pulse of 0.01
Claim 1, which is performed in ~0.1ms
A method for producing colored stainless steel material as described in . （７）前記着色電解液が、５個バナジウムとして、０．
５〜１．５ｍｏｌ／ｌのバナジウム化合物と、５〜１０
ｍｏｌ／ｌの硫酸とを含む混合水溶液であり、前記交番
電流電解が、陽極電流密度０．０１〜０．２Ａ／ｄｍ＾
２、陰極電流密度０．０１〜０．２Ａ／ｄｍ＾２、繰返
し数１０Ｈｚ以下で行われるものであり、 前記パルス電流電解が、１パルスの通電時間が０．０１
〜０．１ｍｓで行われるものである特許請求範囲第１項
に記載の着色ステンレス鋼材の製造方法。(7) The colored electrolyte contains 5 vanadiums and 0.
5 to 1.5 mol/l of vanadium compound, and 5 to 10
It is a mixed aqueous solution containing sulfuric acid of mol/l, and the alternating current electrolysis is performed at an anode current density of 0.01 to 0.2 A/dm^.
2. The pulsed current electrolysis is carried out at a cathode current density of 0.01 to 0.2 A/dm^2 and a repetition rate of 10 Hz or less, and the pulsed current electrolysis is performed with a current conduction time of 1 pulse of 0.01
The method for manufacturing a colored stainless steel material according to claim 1, wherein the coloring is performed in 0.1 ms. （８）前記交番電流電解が交番電流電解槽の対極にステ
ンレス鋼材を用いて行われるものである特許請求の範囲
第１項ないし第７項のいずれかに記載の着色ステンレス
鋼材の製造方法。(8) The method for producing a colored stainless steel material according to any one of claims 1 to 7, wherein the alternating current electrolysis is performed using a stainless steel material as a counter electrode of an alternating current electrolyzer.
JP29923985A 1985-12-28 1985-12-28 Manufacture of colored stainless steel stock Granted JPS62158898A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP29923985A JPS62158898A (en) 1985-12-28 1985-12-28 Manufacture of colored stainless steel stock

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP29923985A JPS62158898A (en) 1985-12-28 1985-12-28 Manufacture of colored stainless steel stock

Publications (2)

Publication Number Publication Date
JPS62158898A true JPS62158898A (en) 1987-07-14
JPH0533320B2 JPH0533320B2 (en) 1993-05-19

Family

ID=17869948

Family Applications (1)

Application Number Title Priority Date Filing Date
JP29923985A Granted JPS62158898A (en) 1985-12-28 1985-12-28 Manufacture of colored stainless steel stock

Country Status (1)

Country Link
JP (1) JPS62158898A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101952624B1 (en) * 2017-08-30 2019-02-27 광화금속(주) Oxidation colorant composition and method for manufacturing the same
KR101952626B1 (en) * 2017-08-30 2019-02-27 광화금속(주) Black oxidation colorant composition and method for manufacturing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101952624B1 (en) * 2017-08-30 2019-02-27 광화금속(주) Oxidation colorant composition and method for manufacturing the same
KR101952626B1 (en) * 2017-08-30 2019-02-27 광화금속(주) Black oxidation colorant composition and method for manufacturing the same

Also Published As

Publication number Publication date
JPH0533320B2 (en) 1993-05-19

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