JPH0230400B2 - SUTENRESUKOZAINORENZOKUCHAKUSHOKUHOHO - Google Patents
SUTENRESUKOZAINORENZOKUCHAKUSHOKUHOHOInfo
- Publication number
- JPH0230400B2 JPH0230400B2 JP20082185A JP20082185A JPH0230400B2 JP H0230400 B2 JPH0230400 B2 JP H0230400B2 JP 20082185 A JP20082185 A JP 20082185A JP 20082185 A JP20082185 A JP 20082185A JP H0230400 B2 JPH0230400 B2 JP H0230400B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- coloring
- alternating current
- electrolysis
- color
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 claims description 31
- 229910001220 stainless steel Inorganic materials 0.000 claims description 31
- 239000010935 stainless steel Substances 0.000 claims description 31
- 238000004040 coloring Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
＜産業上の利用分野＞
本発明は、主要な用途は建材用であるステンレ
ス鋼材の連続着色技術に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to continuous coloring technology for stainless steel materials whose main application is for building materials.
＜従来技術とその問題点＞
ステンレス鋼帯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法が知られている（特公昭52−
32621、特公昭52−25817、特公昭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で、製品としてはバツ
チ式で生産した単板が主なものである。<Prior art and its problems> 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 colors to stainless steel strips (Special Publication No. 52-
32621, Special Publication No. 52-25817, Special Publication No. 53-31817). This method consists of two steps: a "coloring" step and a "hardening" step, each of which is performed using independent solution composition, temperature, and treatment conditions.The product is a veneer produced in batches. The main thing.
また、ステンレス鋼帯を連続的に着色する方法
も開示されている（特公昭60−22065）。この方法
はINCO法に基づく「着色」槽と「硬膜」槽とい
う２液２工程により着色ステンレス鋼板を製造す
るものであり、その色調の制御は「着色」工程で
「着色」槽の鋼帯の行路上の複数個所で対極の白
板との間の電位を測定し、基準点からの電位差で
行うものである。このため、浸漬時間を必然的に
制御せねばならず、常に巻取電動機で通板速度を
変えるという複雑で困難な方式である。なお、色
調は後工程の「硬膜」処理を行えば、変化は不可
避であることから決まつた色調の製品を作るのは
容易ではない。 A method for continuously coloring stainless steel strips is also disclosed (Japanese Patent Publication No. 60-22065). This method is based on the INCO method and produces colored stainless steel sheets using two liquid processes: a "coloring" tank and a "hardening" tank.The color tone is controlled by controlling the steel strip in the "coloring" tank during the "coloring" process. The potential between the counter electrode and the white plate is measured at multiple locations along the path of the electrode, and the potential difference from the reference point is used. For this reason, the dipping time must necessarily be controlled, which is a complicated and difficult method that requires constantly changing the threading speed using the take-up motor. Note that it is not easy to produce products with a fixed color tone because the color tone will inevitably change if a "hardening" process is performed in the post-process.
種々の多彩な着色ステンレス鋼帯を安価に提供
するには、工程の省略化と決まつた色調を再現性
良く出せる方法に基づいた連続ラインによる製造
が必要となる。 In order to provide a variety of colored stainless steel strips at low cost, it is necessary to manufacture them on a continuous line based on a method that can simplify processes and produce a fixed color tone with good reproducibility.
そこで、「着色」、「硬膜」という２工程では上
述したような問題点があるため、「着色」、「硬膜」
を１液１工程で行い得れば、工程が簡略化でき連
続ラインでの着色ステンレス鋼帯の製造が工業上
可能となる。 Therefore, since the two steps of "coloring" and "dural mater" have the problems mentioned above, "coloring" and "dural mater"
If this can be carried out in one liquid and one step, the process can be simplified and it becomes possible to industrially manufacture colored stainless steel strips in a continuous line.
化学着色法によりステンレス鋼表面に生成する
酸化皮膜はCr2O3主体のもので、電気化学的には
陽極電解を行うことにより得られる。また硬膜処
理は着色とは逆に陰極電解を施すことにより多孔
質なCr2O3皮膜を封孔して強化している。 The oxide film formed on the surface of stainless steel by the chemical coloring method is mainly composed of Cr 2 O 3 and can be obtained electrochemically by performing anodic electrolysis. In contrast to coloring, hardening treatment uses cathodic electrolysis to seal and strengthen the porous Cr 2 O 3 coating.
本発明者らは、２モル以上の６価クロムと2.5
モル以上の硫酸を含む混合溶液中において陽極電
解電流密度；0.01〜3.0A／ｄm2、陰極電解電流密
度；0.03〜5.0A／ｄm2、繰返し数；100Hz以下で
陽極電解と陰極電解を交互に繰返す交番電流電解
を行うことを特徴とする化学着色ステンレス鋼材
の製造方法を発明して出願している（特開昭61−
127899号公報参照）。この方法によれば陽極電気
量と陰極電気量を最適に組合せることにより１液
１工程で化学着色ステンレス鋼材を製造できる。 The present inventors have discovered that 2 moles or more of hexavalent chromium and 2.5
In a mixed solution containing more than mol of sulfuric acid, anodic electrolysis and cathodic electrolysis are alternately carried out at an anodic electrolysis current density of 0.01 to 3.0 A/dm 2 , a cathodic electrolysis current density of 0.03 to 5.0 A/dm 2 , and a repetition rate of 100 Hz or less. He invented and applied for a method for manufacturing chemically colored stainless steel material, which is characterized by repeated alternating current electrolysis (Japanese Patent Laid-Open No. 1983-1999).
(See Publication No. 127899). According to this method, a chemically colored stainless steel material can be produced in one liquid and one step by optimally combining the anode electricity amount and the cathode electricity amount.
＜発明の目的＞
本発明はこの方法を前述した交番電流電解法の
連続ラインに適用して、電位と通板速度の制御を
行う従来法とは全く異なる測色データの交番電流
電解条件へのフイードバツクによる全く新規な色
調管理によつてステンレス鋼材に連続着色すると
いう全く新しい方法を提供しようとすることにあ
る。<Purpose of the Invention> The present invention applies this method to the continuous line of the above-mentioned alternating current electrolysis method to apply the colorimetric data to the alternating current electrolysis conditions, which is completely different from the conventional method of controlling the potential and the threading speed. The purpose of this invention is to provide a completely new method of continuously coloring stainless steel materials using completely new color tone management using feedback.
＜発明の構成＞
すなわち、本発明は、ステンレス鋼材を交番電
流電解法により連続着色するにあたり、交番電流
電解槽の着色鋼材出側に設けた色識別センサーに
より色着を検出し、制御コンピユーターを介し
て、該検出値に応じて、該電解槽の電解条件を調
整することを特徴とするステンレス鋼材の連続着
色方法を提供するものである。<Structure of the Invention> That is, the present invention, when continuously coloring stainless steel materials by an alternating current electrolytic method, detects the coloring by a color identification sensor provided on the outlet side of the colored steel material of an alternating current electrolytic cell, and detects the coloring through a control computer. Accordingly, there is provided a continuous coloring method for stainless steel material, which is characterized in that the electrolytic conditions of the electrolytic cell are adjusted according to the detected value.
以下に本発明を更に詳細に説明する。 The present invention will be explained in more detail below.
交番電流電解法を用いて連続的にステンレス鋼
材に着色処理を施すラインの１例を第１図に示
す。 FIG. 1 shows an example of a line that continuously colors stainless steel materials using alternating current electrolysis.
ここでいうステンレス鋼材とは、線材、管材、
板材、塊、異形断面図、粉粒体など任意の形状で
よいが、以下の説明は代表的に鋼帯について行
う。 Stainless steel materials here include wire rods, pipe materials,
Although any shape may be used, such as a plate, a lump, a modified cross-sectional view, or a granular material, the following description will be made with reference to a steel strip as a representative example.
第１図に示すように、ステンレス鋼帯１はアン
コイラー２から巻き出されて前処理装置３で表面
に付着した油等の汚れが除去され、均一な表面と
なつた後コンダクターロール４を通つて、交番電
流電解槽５に導かれる。この槽には対極板６があ
り、これとステンレス鋼帯１の間で交番電流電解
を行い、着色処理されて、この電解槽５から出て
いく。 As shown in FIG. 1, a stainless steel strip 1 is uncoiled from an uncoiler 2, and a pre-treatment device 3 removes dirt such as oil adhering to the surface to give it a uniform surface. After that, it is passed through a conductor roll 4. , is led to an alternating current electrolyzer 5. This tank has a return electrode plate 6, and alternating current electrolysis is performed between this and the stainless steel strip 1, and the strip is colored and leaves the electrolytic tank 5.
本発明においては、この電解槽５の出口のガイ
ドロール７付近に色識別センサー８を設置し、こ
れにより着色後のステンレス鋼板の色調測定を行
う。この色調測定に際しては、ステンレス鋼帯１
上の処理液を例えば加圧空気で除去するのがよ
い。 In the present invention, a color identification sensor 8 is installed near the guide roll 7 at the outlet of the electrolytic cell 5, and the color tone of the colored stainless steel plate is measured using this sensor. For this color tone measurement, stainless steel strip 1
It is preferable to remove the upper processing liquid using, for example, pressurized air.
得られた色調測定データ（色彩の表示はJIS
Z8730で色差を用いるのがよい）は、制御コンピ
ユーター９に入力される。ここで予め設定した色
差の限界を越えている場合は、陽極電解・陰極電
解の電流密度および各々の電解時間、電解繰返し
数、浴温度などの電解条件にフイードバツクさせ
て着色処理の制御を行う。図面には、電解条件と
して電流ｉ、電解時間ｔ、電解繰返し数Ｎを示
す。この際必ずしも従来のように通板速度を変化
せしむる必要はない。 Obtained color tone measurement data (color display is JIS
Z8730 (preferably using color difference) is input to the control computer 9. If the color difference exceeds the preset limit, the coloring process is controlled by feedback to the electrolytic conditions such as the current density of anodic electrolysis and cathodic electrolysis, each electrolysis time, number of electrolysis cycles, and bath temperature. In the drawing, current i, electrolysis time t, and number of electrolysis repetitions N are shown as electrolysis conditions. At this time, it is not necessarily necessary to change the sheet passing speed as in the conventional method.
このようにして予定通りの色調に仕上つたステ
ンレス鋼帯１は後続の後処理装置１０を経て巻取
機１１に巻取られる。 The stainless steel strip 1, which has been finished in the desired color tone in this manner, is passed through a subsequent post-processing device 10 and then wound up by a winding machine 11.
交番電流電解槽５にはステンレス鋼帯１の両方
の面に対向する対極板６を動作させることにより
ステンレス鋼帯１の両面着色を、あるいはステン
レス鋼帯１の一方の面に対向する対極板６を動作
させることによりステンレス鋼帯１の片面発色も
可能である。 In the alternating current electrolyzer 5, the stainless steel strip 1 can be colored on both sides by operating the counter electrode plates 6 facing both sides of the stainless steel strip 1, or the counter electrode plate 6 facing one side of the stainless steel strip 1 can be colored. It is also possible to color one side of the stainless steel strip 1 by operating the .
以上の如く、従来法にない交番電流電解法によ
る１液１工程で、新規な色識別センサーによる色
調管理法により連続的にステンレス鋼帯を安定し
てNBS単位（0.92×E*ab）で1.0以下の着色状態
とし得ることができる。E*abとは下記のものを
意味する。 As described above, stainless steel strips can be continuously and stably produced in NBS units (0.92 x E * ab) with a one-liquid, one-step process using an alternating current electrolysis method using a new color discrimination sensor. The following colored states can be obtained. E * ab means:
E*abは、色差計（ミノルタCR−100）にて、
CIE（国際照明委員会）1976年推奨の（L*a*b*）
表示系に基づき、算定したものである。 E * ab is measured using a color difference meter (Minolta CR-100).
CIE (International Commission on Illumination) 1976 recommendation (L * a * b * )
Calculated based on display system.
＜実施例＞
第１図に示す装置を用いて交番電流電解を行う
際、交番電流電解槽の溶液として成分は（250
ｇ／無水クロム酸＋500ｇ／硫酸）で温度60
℃±２℃としたものを用いて、制御コンピユータ
ーに入力した条件、即ち陽・陰極電流密度を各
0.5A／ｄm2、陽・陰極電解時間を各３秒（繰返
し数0.16Hz）で通板速度10cm／minにて
SUS304BA（光輝焼鈍）処理鋼帯を用いて着色処
理を行つた。電極長さは100cmとした。<Example> When performing alternating current electrolysis using the apparatus shown in Fig. 1, the components of the solution in the alternating current electrolyzer were (250
g/chromic anhydride + 500 g/sulfuric acid) at a temperature of 60
℃±2℃, and the conditions input into the control computer, that is, the anode and cathode current densities, were
0.5A/dm 2 , anode and cathode electrolysis times of 3 seconds each (repetition rate 0.16Hz), and a threading speed of 10cm/min.
Coloring treatment was performed using SUS304BA (bright annealing) treated steel strip. The electrode length was 100 cm.
比較としては、80℃における浸漬、即ち通板速
度を変えて着色させる方法をとつた。溶液成分は
同一で通板速度は５〜10cm／minとした。 For comparison, we used a method of immersion at 80°C, that is, a method of coloring by changing the plate passing speed. The solution components were the same, and the plate passing speed was 5 to 10 cm/min.
このような条件でステンレス鋼帯は青色の色調
を呈する。そこで両方法で得られた着色ステンレ
ス鋼帯１ｍの中で10cm毎に９点JIS Z8730に規定
されている色差測定を行つた。 Under these conditions, the stainless steel strip takes on a blue hue. Therefore, within 1 m of the colored stainless steel strip obtained by both methods, color difference measurements were carried out at 9 points every 10 cm as specified in JIS Z8730.
その結果、本発明例では色差△Ｅは0.2以内で
あつたのに対して、比較例では色差△Ｅは約3.5
であつた。 As a result, the color difference △E was within 0.2 in the inventive example, while the color difference △E was approximately 3.5 in the comparative example.
It was hot.
また、目視判定を行つても、本発明例では色の
差は認められず、発色処理の均一性は、極めて高
かつたが、比較例ではほぼ全体に渡つて青色にな
つてるが、特に端部にかなりの色ムラが認められ
た。さらに、比較例ではこの後、硬膜処理を行つ
たが、この工程でも色調が変化した。 In addition, even when visually judged, no difference in color was observed in the inventive example, and the uniformity of the coloring process was extremely high, but in the comparative example, almost the entire area was blue, but especially at the edges. Considerable color unevenness was observed in the area. Further, in the comparative example, a hardening treatment was performed after this, but the color tone changed even in this step.
＜発明の効果＞
本発明によれば、着色処理後の色調を測定し
て、この測定値に応じて着色電解処理条件を制御
するので色調の一定した着色ステンレス鋼材を連
続的に従来法より簡単な方式で安定して生産で
き、工業的に安価で多彩な色調の製品を安定して
多量に提供することができる。<Effects of the Invention> According to the present invention, since the color tone after coloring treatment is measured and the coloring electrolytic treatment conditions are controlled according to the measured value, it is easier to continuously produce colored stainless steel materials with a constant color tone than with conventional methods. It can be produced stably using a method that allows for stable production of industrially inexpensive products in a variety of colors in large quantities.
第１図はステンレス鋼帯を交番電流電解法によ
り連続的に発色処理する工程を示す線図である。
符号の説明、１……ステンレス鋼帯、２……ア
ンコイラー、３……前処理装置、４……コンダク
ターロール、５……交番電流電解槽、６……対極
板、７……ガイドロール、８……色識別センサ
ー、９……制御コンピユーター、１０……後処理
装置、１１……巻取機。
FIG. 1 is a diagram showing the process of continuously coloring a stainless steel strip by alternating current electrolysis. Explanation of symbols, 1... Stainless steel strip, 2... Uncoiler, 3... Pretreatment device, 4... Conductor roll, 5... Alternating current electrolyzer, 6... Return electrode, 7... Guide roll, 8 ... Color identification sensor, 9 ... Control computer, 10 ... Post-processing device, 11 ... Winding machine.
Claims (1)
着色するにあたり、交番電流電解槽の着色鋼材出
側に設けた色識別センサーにより色差を検出し、
制御コンピユーターを介して、該検出値に応じ
て、該電解槽の電解条件を調整することを特徴と
するステンレス鋼材の連続着色方法。1. When continuously coloring stainless steel materials by alternating current electrolytic method, the color difference is detected by a color identification sensor installed on the colored steel material outlet side of the alternating current electrolytic cell,
A continuous coloring method for stainless steel material, characterized in that the electrolytic conditions of the electrolytic cell are adjusted according to the detected value via a control computer.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20082185A JPH0230400B2 (en) | 1985-09-11 | 1985-09-11 | SUTENRESUKOZAINORENZOKUCHAKUSHOKUHOHO |
| US06/887,020 US4859287A (en) | 1984-11-22 | 1985-11-22 | Method for producing colored stainless steel stock |
| DE8585905888T DE3583142D1 (en) | 1984-11-22 | 1985-11-22 | METHOD FOR PRODUCING COLORED STAINLESS STEEL MATERIALS AND DEVICE FOR THEIR CONTINUOUS PRODUCTION. |
| PCT/JP1985/000647 WO1986003229A1 (en) | 1984-11-22 | 1985-11-22 | Method of manufacturing colored stainless steel materials and apparatus for continuously manufacturing same |
| EP85905888A EP0204846B1 (en) | 1984-11-22 | 1985-11-22 | Method of manufacturing colored stainless steel materials and apparatus for continuously manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20082185A JPH0230400B2 (en) | 1985-09-11 | 1985-09-11 | SUTENRESUKOZAINORENZOKUCHAKUSHOKUHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6260893A JPS6260893A (en) | 1987-03-17 |
| JPH0230400B2 true JPH0230400B2 (en) | 1990-07-05 |
Family
ID=16430761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20082185A Expired - Lifetime JPH0230400B2 (en) | 1984-11-22 | 1985-09-11 | SUTENRESUKOZAINORENZOKUCHAKUSHOKUHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0230400B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09165696A (en) * | 1995-12-14 | 1997-06-24 | Toyama Keikinzoku Kogyo Kk | Method for electrolytically coloring aluminum or aluminum alloy |
| CN111188068A (en) * | 2020-01-17 | 2020-05-22 | 肇庆宏旺金属实业有限公司 | Black titanium plating method for whole roll of stainless steel |
-
1985
- 1985-09-11 JP JP20082185A patent/JPH0230400B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6260893A (en) | 1987-03-17 |
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