JPH0230390B2 - SUTENRESUKONOCHAKUSHOKUTEISHIHO - Google Patents
SUTENRESUKONOCHAKUSHOKUTEISHIHOInfo
- Publication number
- JPH0230390B2 JPH0230390B2 JP15399381A JP15399381A JPH0230390B2 JP H0230390 B2 JPH0230390 B2 JP H0230390B2 JP 15399381 A JP15399381 A JP 15399381A JP 15399381 A JP15399381 A JP 15399381A JP H0230390 B2 JPH0230390 B2 JP H0230390B2
- Authority
- JP
- Japan
- Prior art keywords
- coloring
- stainless steel
- colored
- stopping
- reaction
- 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
- 238000004040 coloring Methods 0.000 claims description 92
- 229910001220 stainless steel Inorganic materials 0.000 claims description 62
- 239000010935 stainless steel Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 238000010186 staining Methods 0.000 claims 4
- 239000000463 material Substances 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 34
- 235000019646 color tone Nutrition 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000003086 colorant Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910000599 Cr alloy Inorganic materials 0.000 description 3
- 239000000788 chromium alloy Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- -1 blue Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Electrochemical Coating By Surface Reaction (AREA)
Description
本発明は着色液中で着色反応を急速に停止させ
ることによつて一定の目標色に対し色差の少ない
色調を再現性良く得られる着色ステンレス鋼の製
造におけるステンレス鋼の着色停止法に関するも
のである。
近年ステンレス鋼を着色する技術が急速な進歩
を遂げ数多くの特許が公開される様になつて来
た。中でも特開昭48−11243「クロム合金の処理
法」と特開昭49−21339「クロム合金の処理」によ
るカラーステンレス鋼の製造方法は所望の着色の
再現性が得られること、耐摩耗性が良いことなど
の特徴があり、工業的生産の場合はこの方法が用
いられている。上記発明のうち着色度合の再現性
については特開昭48−11243に詳細に述べられて
いる。この内容はクロム酸と硫酸との混合水溶液
中にステンレス鋼を浸漬し、ステンレス鋼の表面
と参照電極（飽和甘汞電極または白金電極）間の
電位差を監視し、所望の着色に達した時の電位差
が第１図の着色電位と時間との関係曲線において
変曲点電位Ａから所望電位差Ｂ−Ａに変化したと
きにステンレス鋼を着色反応系外に取り出すこと
によつて着色反応を停止させる従来の着色制御法
による上記問題点を解決すべく本発明者が鋭意研
究を重ねた結果、着色終了の合図から着色反応が
完全に停止するまでの時間的バラツキが色調の再
源性に何等関与しない着色停止法として、着色液
中においても着色反応を停止させることが可能な
ステンレス鋼の着色停止法を見出し本発明を成す
に至つたのである。
また特開昭49−21339「クロム合金の処理」には
着色処理中に着色し様とするステンレス鋼がアノ
ードになる様に直流電流を印加した状態で特開昭
48−11243と同様に参照電極とステンレス鋼との
電位差を監視し所望の電位差になつたとき直流電
解を停止させ、一層正確な電位差の指標を得よう
とするものである。
しかしながら、この方法においても被着色ステ
ンレス鋼が着色液中に浸漬されている状態では着
色反応は常に進行している。またこの方法と本発
明方法とは外部より通電することについては同様
であるが、次の点が異なつている。特開昭49−
21339ではステンレス鋼を陽極（アノード）とし
て着色処理中に通電するに対し、本発明方法では
着色処理中はステンレス鋼に通電せずに着色の終
了した時点でステンレス鋼に外部電圧を印加して
カソードにする着色反応の停止方法を開示するも
のである。
本発明の要旨はステンレス鋼の着色色調の再現
性を向上させるため着色終了の合図によつて直ち
に着色液中で着色反応を停止させる着色停止法で
ある。
着色反応系においてはステンレス鋼表面ではア
ノード反応及びカソード反応の両者が絶えず起つ
ていると考えられている。
通常ステンレス鋼の着色酸化皮膜はアノード反
応が優勢であるために形成されるものである。
そこで着色電位が所望の設定電位差に到達する
と同時に予め着色材をカソードになる様に設定し
た別回路を設け、一定の電位を得るべく外部電圧
を印加する。即ち、前述のアノード酸化反応系に
対してカソード還元反応系を強制的に導入するこ
とで、この優勢な着色酸化反応を還元反応により
打ち消し、両反応量のバランスを平衝に保持する
のである。之により着色反応は停止し着色液中で
も着色の進行を停止させ再現性の良好な色調を得
様とするものである。本発明はこの様にしてステ
ンレス鋼の着色処理を行なうことにより色差の少
ない再現性の良い着色処理が可能になる。本発明
の適用範囲はオーステナイト系、フエライト系及
び各種表面仕上（BA仕上、HL仕上）のステン
レス鋼に適用可能であり、この処理方法により着
色反応の停止が可能である。
次に本発明を詳細に説明する。
無水クロム酸（250ｇ／）と硫酸（500ｇ／
）とを含む水溶液を80℃に加熱した着色液中に
参照電極（Pt）と対極（Pt）とをセツトし、ス
テンレス鋼を浸漬し着色処理した。なお、対極は
着色溶液に不溶性であることが望ましくPt、Ti、
Pb、Ag板の何れもが使用可能である。先ず、参
照電極に対するステンレス鋼の電位を管理し所望
の着色電位差に到達させ直ちに外部の定電位定電
流発生装置から対極に対して着色液中のステンレ
ス鋼をカソードにするため印加した。
そして、この状態で電位、電流を記録針で計測
しながら一定時間保持した。この後被着色材であ
るステンレス鋼を着色液から取り出し水洗、硬膜
処理後乾燥させた。色の測定はカラーアナライザ
〔(株)日立製作所207型 ライトデイフエーザー
BaSO4白板標準〕を使用しJIS Z8722の条件を
準拠して行なつた。
以下本発明の実施例を示す。
供試材はSUS304ステンレス鋼のヘアーライン
研摩材（HL仕上 1.5mm×50mm×100mm）を使用
し、前述の着色処理条件により着色させた。そし
て、グリーンの色調を得るべく第１図のＢ−Ａの
着色電位差を19.5ｍＶに設定した。着色電位差が
19.5ｍＶに到達すると同時に対極に対してステン
レス鋼をカソードにせしめるべく外部から定電位
定電流発生装置により印加した。このときの着色
電位の変化を第２図に示す。着色電位差Ｂ−Ａが
19.5ｍＶに達すると同時に外部からステンレス鋼
をカソードにせしめるべく定電圧を印加すると、
ステンレス鋼と参照電極との間の電位差は急激に
低下した。
そこで、この状態を２分間保持しステンレス鋼
を着色液から取り出し硬膜処理後、乾燥させた。
一方、本発明による処理効果を従来法と比較する
ために着色電位差を19.5ｍＶに到達させ直ちにス
テンレス鋼を着色液から取り出し硬膜処理後乾燥
させた。この本発明による処理材と従来法による
処理材（比較材）とをカラーアナライザにより測
色した結果をａ値、ｂ値のクロマチイツクネス指
数特性曲線図として第３図に示す。
図中の曲線の矢印は着色反応の進行を示す。
この結果、ステンレス鋼と参照電極間の電位差
を−400ｍＶ〜−210ｍＶの範囲にするため外部電
圧を印加した着色処理材（No.５〜No.11）は着色反
応が抑制され比較材（No.13、No.14）と同程度の色
調を示し、着色反応が停止することが判明した。
之に対して外部電圧を印加せずに着色液中に２分
間保持した着色処理剤（No.１）は着色反応が大き
く進行し比較材（No.13、No.14）とはかけ離れた色
調を示し、ステンレス鋼表面はパウダリングを起
こした。また、ステンレス鋼と参照電極間の電位
差が−205ｍＶ〜−180ｍＶの範囲になる様に外部
電圧を印加した着色処理材（No.４〜No.２）はNo.１
と較べ着色反応はNo.５〜No.11と同様に着色反応が
可成り抑制されはするが、比較材（No.13、No.14）
よりも若干進行していることが判明した。更に−
450ｍＶにせしめるべく外部電圧を印加した着色
処理材（No.12）は比較材と較べ色調は後退し、既
に形成された着色酸化皮膜の破壊が進行している
ことが判明した。
以上の結果から、ステンレス鋼をカソードにせ
しめるべく外部電圧を印加し着色反応を停止させ
る着色処理において着色反応を停止させることの
出来るステンレス鋼と参照電極との電位差は−
400ｍＶ〜−210ｍＶの範囲であり、−300ｍＶ〜−
260ｍＶの範囲が所望の着色電位に到達すると同
時に着色液から取り出した着色材（比較材）とほ
ぼ同等の色調を得ることの出来る好ましい範囲で
あることが判明した。
以上の実施例の結果を基に
(1) グリーン以外の色調でも前述の実施例と同様
にステンレス鋼と参照電極との電位差が−300
ｍＶ〜−260ｍＶの同範囲で着色反応の停止が
可能か
(2) SUS304ステンレス鋼の光輝焼鈍材（BA仕
上材）についても前述のHL仕上材の着色反応
停止条件で停止が可能か
(3) 本発明の着色停止法で良好な着色再現性を得
ることが可能か
の３点について実験を行なつた。このことを以下
の実施例で説明する。
着色液は前述の実施例の条件と同様である。供
試材はHL仕上材（1.5mm×50mm×100mm）、BA仕
上材（0.4mm×50mm×150mm）である。そして第１
図の着色電位差Ｂ−Ａを6.0ｍＶ、13.0ｍＶ、15.0
ｍＶ、19.5ｍＶに設定しブルー、ゴールド、レツ
ド、グリーンの４色について各々10枚着色させ
た。
着色反応停止処理材として前述の実施例を基に
ステンレス鋼と参照電極間の電位差を−300ｍＶ
〜−260ｍＶの範囲に設定し１分間保持させた。
また、第１図の着色電位差Ｂ−Ａに到達させると
同時に着色液より取り出した処理材を比較材とし
た。之等の処理材の測定結果をａ値、ｂ値のクロ
マチイツクネス指数特性曲線図として第４図に示
す。ステンレス鋼と参照電極との間の電位差が−
300ｍＶ〜−260ｍＶの範囲ではブルー、ゴール
ド、レツド、グリーンの４色共に比較材とほぼ同
程度の色調を示し、各色調とも着色反応が停止す
ることが判明した。また、BA仕上材とHL仕上
材とを比較した場合、表面形状に影響されてクロ
マチイツクネス指数曲線の軌跡は異なり、BA仕
上材がHL仕上材よりもａ値、ｂ値共に絶対値で
大きな値を示し色彩は彩やかになるが、BA仕上
材はHL仕上材と同様に−300ｍＶ〜−260ｍＶの
電位差の範囲で比較材とほ同等の色調を示し着色
反応を停止させることが判明した。更に各色調の
着色処理材10枚の測色結果から、色のバラツキの
程度を確認するためにＬ値、ａ値、ｂ値の標準偏
差値を第１表に示した。
The present invention relates to a method for stopping the coloring of stainless steel in the production of colored stainless steel, which can obtain color tones with little color difference for a certain target color with good reproducibility by rapidly stopping the coloring reaction in a coloring liquid. . In recent years, the technology for coloring stainless steel has made rapid progress and many patents have been published. Among them, the methods for producing colored stainless steel based on JP-A No. 48-11243 "Processing of Chromium Alloys" and JP-A No. 49-21339 "Processing of Chromium Alloys" are capable of obtaining the desired reproducibility of coloring and have excellent wear resistance. This method is used in industrial production due to its good characteristics. Among the above inventions, the reproducibility of the degree of coloring is described in detail in JP-A-11243-1983. This involves immersing stainless steel in a mixed aqueous solution of chromic acid and sulfuric acid, monitoring the potential difference between the surface of the stainless steel and a reference electrode (a saturated acetate electrode or a platinum electrode), and measuring when the desired coloration is reached. Conventionally, the coloring reaction is stopped by taking the stainless steel out of the coloring reaction system when the potential difference changes from the inflection point potential A to the desired potential difference B-A in the coloring potential vs. time relationship curve shown in FIG. As a result of intensive research by the present inventor to solve the above-mentioned problems with the coloring control method, it was found that the time variation from the signal of completion of coloring to the complete stop of the coloring reaction does not have any influence on the regenerability of the color tone. As a method for stopping coloring, the present invention was achieved by discovering a method for stopping coloring of stainless steel that can stop the coloring reaction even in a colored liquid. In addition, in JP-A No. 49-21339 ``Treatment of Chromium Alloys'', a direct current was applied to the stainless steel that was to be colored during the coloring process so that it became an anode.
Similar to No. 48-11243, this method monitors the potential difference between the reference electrode and stainless steel, and stops direct current electrolysis when the desired potential difference is reached, in order to obtain a more accurate index of the potential difference. However, even in this method, the coloring reaction is always progressing while the stainless steel to be colored is immersed in the coloring liquid. Furthermore, although this method and the method of the present invention are similar in that they are energized from outside, they differ in the following points. Japanese Patent Application Publication 1973-
In 21339, the stainless steel is used as an anode and electricity is applied during the coloring process, whereas in the method of the present invention, no electricity is applied to the stainless steel during the coloring process, and when coloring is completed, an external voltage is applied to the stainless steel to create the cathode. The present invention discloses a method for stopping a coloring reaction. The gist of the present invention is a coloring stop method that immediately stops the coloring reaction in a coloring solution upon a signal indicating the end of coloring, in order to improve the reproducibility of the color tone of stainless steel. In the coloring reaction system, both anode and cathode reactions are thought to constantly occur on the stainless steel surface. Usually, a colored oxide film on stainless steel is formed due to a predominant anodic reaction. Therefore, as soon as the coloring potential reaches a desired set potential difference, a separate circuit is provided in which the coloring material is set to become a cathode, and an external voltage is applied to obtain a constant potential. That is, by forcibly introducing the cathode reduction reaction system to the anodic oxidation reaction system described above, this dominant coloring oxidation reaction is canceled out by the reduction reaction, and the balance between the amounts of both reactions is maintained at equilibrium. This stops the coloring reaction and stops the progress of coloring even in the coloring solution, making it possible to obtain a color tone with good reproducibility. By coloring stainless steel in this manner, the present invention enables coloring treatment with little color difference and good reproducibility. The scope of the present invention is applicable to austenitic stainless steel, ferrite stainless steel, and stainless steel with various surface finishes (BA finish, HL finish), and the coloring reaction can be stopped by this treatment method. Next, the present invention will be explained in detail. Chromic anhydride (250g/) and sulfuric acid (500g/
) A reference electrode (Pt) and a counter electrode (Pt) were set in a colored solution containing an aqueous solution heated to 80°C, and the stainless steel was immersed and colored. The counter electrode is preferably insoluble in the colored solution, such as Pt, Ti,
Both Pb and Ag plates can be used. First, the potential of the stainless steel with respect to the reference electrode was controlled to reach a desired coloring potential difference, and immediately a voltage was applied from an external constant potential constant current generator to the counter electrode in order to make the stainless steel in the coloring liquid a cathode. Then, this state was maintained for a certain period of time while measuring the potential and current with a recording needle. Thereafter, the stainless steel material to be colored was taken out from the coloring solution, washed with water, hardened, and dried. Color measurement is done using a color analyzer [Hitachi, Ltd. Model 207 Light Dephaser]
BaSO 4 white board standard] was used in accordance with the conditions of JIS Z8722. Examples of the present invention will be shown below. The test material used was SUS304 stainless steel hairline abrasive material (HL finish 1.5 mm x 50 mm x 100 mm), which was colored according to the coloring treatment conditions described above. In order to obtain a green tone, the coloring potential difference between B and A in FIG. 1 was set to 19.5 mV. colored potential difference
At the same time when 19.5 mV was reached, voltage was applied from the outside using a constant potential constant current generator to make the stainless steel a cathode for the counter electrode. FIG. 2 shows the change in coloring potential at this time. The colored potential difference B-A is
As soon as the voltage reaches 19.5mV, a constant voltage is applied externally to make the stainless steel become a cathode.
The potential difference between the stainless steel and reference electrode dropped rapidly. Therefore, this state was maintained for 2 minutes, and the stainless steel was taken out from the coloring solution, hardened, and dried.
On the other hand, in order to compare the treatment effect of the present invention with the conventional method, the stainless steel was immediately removed from the coloring solution after the coloring potential difference reached 19.5 mV and dried after hardening. The results of color measurement of the treated material according to the present invention and the conventionally treated material (comparative material) using a color analyzer are shown in FIG. 3 as a chromaticity index characteristic curve diagram of a value and b value. The curved arrows in the figure indicate the progress of the coloring reaction. As a result, the coloring reaction of the colored materials (No. 5 to No. 11) to which an external voltage was applied to bring the potential difference between the stainless steel and the reference electrode to a range of -400 mV to -210 mV was suppressed, and that of the comparative material (No. 1). 13, No. 14), and the coloring reaction was found to have stopped.
The coloring agent (No. 1), which was kept in the coloring solution for 2 minutes without applying an external voltage, underwent a significant coloring reaction and had a color tone that was far different from that of the comparative materials (No. 13 and No. 14). , and powdering occurred on the stainless steel surface. In addition, the colored materials (No. 4 to No. 2) to which an external voltage was applied so that the potential difference between the stainless steel and the reference electrode was in the range of -205 mV to -180 mV were No. 1.
Compared to the comparative materials (No. 13, No. 14), the color reaction is considerably suppressed, similar to No. 5 to No. 11.
It turned out that it was a little more advanced. Furthermore-
It was found that the colored material (No. 12) to which an external voltage of 450 mV was applied had a regressed color tone compared to the comparative material, and that the already formed colored oxide film was being destroyed. From the above results, the potential difference between the stainless steel and the reference electrode that can stop the coloring reaction in the coloring process where an external voltage is applied to stop the coloring reaction to make the stainless steel a cathode is -
The range is 400mV to -210mV, and -300mV to -
It has been found that a range of 260 mV is a preferable range in which a desired coloring potential can be reached and at the same time, a color tone substantially equivalent to that of the coloring material (comparative material) taken out from the coloring solution can be obtained. Based on the results of the above examples, (1) Even in colors other than green, the potential difference between the stainless steel and the reference electrode is -300
Is it possible to stop the coloring reaction in the same range from mV to -260mV (2) Is it possible to stop the coloring reaction of bright annealed SUS304 stainless steel (BA finished material) using the above-mentioned coloring reaction stopping conditions for HL finished material (3) Experiments were conducted on three points to determine whether it is possible to obtain good coloring reproducibility using the coloring stopping method of the present invention. This will be explained in the following example. The conditions for the coloring liquid were the same as in the previous example. The test materials are HL finish material (1.5 mm x 50 mm x 100 mm) and BA finish material (0.4 mm x 50 mm x 150 mm). and the first
The colored potential difference B-A in the figure is 6.0mV, 13.0mV, 15.0
mV was set to 19.5 mV, and 10 sheets each were colored in four colors: blue, gold, red, and green. As a coloring reaction stop treatment material, the potential difference between the stainless steel and the reference electrode was set to -300 mV based on the above example.
It was set to a range of ~-260 mV and held for 1 minute.
In addition, a treated material taken out from the colored solution at the same time as the coloring potential difference B-A in FIG. 1 was reached was used as a comparison material. The measurement results of these treated materials are shown in FIG. 4 as a chromaticity index characteristic curve diagram of a value and b value. The potential difference between the stainless steel and the reference electrode is −
It was found that in the range of 300 mV to -260 mV, all four colors, blue, gold, red, and green, showed almost the same color tone as the comparative material, and the coloring reaction stopped in each color tone. In addition, when comparing the BA finished material and the HL finished material, the trajectory of the chromaticity index curve is different due to the influence of the surface shape, and the BA finished material has a larger absolute value of both a and b values than the HL finished material. However, like the HL finish material, it was found that the BA finish material showed almost the same color tone as the comparison material within the potential difference range of -300mV to -260mV and stopped the coloring reaction. . Further, from the color measurement results of 10 colored treated materials of each color tone, the standard deviation values of L value, a value, and b value are shown in Table 1 in order to confirm the degree of color variation.
【表】
この表よりステンレス鋼と参照電極との間の電
位差を所望のＢ−Ａに到達させ直ちに着色液より
取り出した着色処理材（比較材）よりもＢ−Ａの
電位差に到達させ直ちに−300ｍＶ〜−260ｍＶに
せしめるべく外部電圧を印加し、この状態を１分
間保持後、着色液より取り出した着色処理材の方
が標準偏差値は小さく、バラツキの少ない良好な
色調の再現性を示すことが判明した。
以上の判明した事象を纒めると、着色液中のス
テンレス鋼と参照電極との間の電位差を所望のＢ
−Ａに到達させ直ちにステンレス鋼を参照電極と
の間でカソードにせしめるべくステンレス鋼と対
極との間に定電圧を印加し、ステンレス鋼を参照
電極に対して−300ｍＶ〜−260ｍＶの範囲に保持
させれば着色反応の進行は停止することが判明し
た。
本発明による処理材は所望の着色電位Ｂ−Ａに
到達させ直ちに着色液から取り出した従来の着色
処理材とほぼ同等の色調を有し、その色調のバラ
ツキは従来の着色処理材よりも小さく良好な色調
の再現性を示すことが判明した。
そして、本発明による処理材はステンレス鋼の
表面仕上（HL仕上、BA仕上）や色調と無関係
であることも判明した。
従来はステンレス鋼の着色反応を停止させる方
法としてステンレス鋼を着色液から取り出し直ち
に水洗を行なつている。
この方法は
(1) 着色液をステンレス鋼表面から除去する
(2) ステンレス鋼の表面温度を低下させる
ことにある。しかしこの方法は
(1) 着色液からステンレス鋼を取り出す速度
(2) 外気温度
(3) 板の厚さ、大きさ（熱容量）
(4) 水洗されるまでの時間
などに影響されて実際に着色反応が停止するまで
の時間に可成りバラツキがあつた。このため一定
の色調を得るのが困難であつた。本発明は色調の
再現性を向上させるために着色液中において着色
反応を停止させるものである。その方法は着色液
中で所望の着色電位に到達すると同時にステンレ
ス鋼がカソードとなる様に外部電圧を印加するの
である。この方法により着色反応を着色液中でも
停止させることが可能となり、従来の方法に較べ
良好な色調の再現性を得ることが可能となつた。
（実施例参照）この着色処理法により着色反応の
停止はもとより促進、遅延、後退（着色皮膜の剥
離）再着色処理の可能性が生まれ色調の再現性が
向上し、処理時間の短縮、処理材の節約新製造技
術の応用などの効果が考えられる。[Table] From this table, the potential difference between the stainless steel and the reference electrode reaches the desired B-A, and then immediately reaches a potential difference of B-A compared to the colored material (comparative material) taken out from the colored solution. After applying an external voltage to 300mV to -260mV and maintaining this state for 1 minute, the colored material taken out from the colored solution has a smaller standard deviation value and shows good color tone reproducibility with less variation. There was found. To summarize the above findings, the potential difference between the stainless steel in the colored liquid and the reference electrode can be adjusted to the desired B.
Immediately after reaching −A, a constant voltage is applied between the stainless steel and the counter electrode to make the stainless steel a cathode with the reference electrode, and the stainless steel is maintained in the range of −300 mV to −260 mV with respect to the reference electrode. It has been found that the progress of the coloring reaction can be stopped if this is done. The treated material according to the present invention has almost the same color tone as the conventional colored treated material that is taken out from the coloring solution immediately after reaching the desired coloring potential B-A, and the variation in color tone is smaller and better than the conventional colored treated material. It was found that the color tone reproducibility was excellent. It was also found that the treated material according to the present invention has no relation to the surface finish (HL finish, BA finish) or color tone of stainless steel. Conventionally, as a method of stopping the coloring reaction of stainless steel, the stainless steel is removed from the coloring solution and immediately washed with water. This method consists of (1) removing the colored liquid from the stainless steel surface, and (2) lowering the surface temperature of the stainless steel. However, with this method, the actual coloring is affected by (1) the speed at which the stainless steel is removed from the coloring liquid, (2) the outside temperature, (3) the thickness and size of the plate (heat capacity), and (4) the time it takes to wash with water. There was considerable variation in the time it took for the reaction to stop. For this reason, it was difficult to obtain a constant color tone. The present invention is to stop the coloring reaction in the coloring liquid in order to improve the reproducibility of color tone. The method involves applying an external voltage so that the stainless steel becomes a cathode at the same time as the desired coloring potential is reached in the coloring solution. This method makes it possible to stop the coloring reaction even in the coloring liquid, making it possible to obtain better color tone reproducibility than conventional methods.
(See Examples) This coloring treatment method not only stops the coloring reaction, but also accelerates, delays, and regresses (peeling off the colored film), creating the possibility of recoloring, improving color reproducibility, shortening processing time, and processing materials. Effects such as the application of new manufacturing technology can be considered.
第１図は着色処理の電位−時間曲線図、第２図
は本発明による着色停止反応の電位−時間曲線
図、第３図は本発明による処理材の測色結果のク
ロマチイツクネス指数特性曲線図であり、第４図
は本発明による処理材の測色結果のクロマチイツ
クネス指数特性曲線図である。図中、
Ａ：変曲点電位、Ｂ：着色終了点電位、Ｂ−
Ａ：着色電位差、Ｃ：外部電圧付与後の着色電
位、１：着色終了点電位に到達後、その儘２分間
保持した処理材、２：着色終了点電位に到達後、
参照電極に対するステンレス鋼の電位を−180ｍ
Ｖに２分間保持した処理材、３：同上、−200ｍＶ
の処理材、４：同上、−205ｍＶの処理材、５〜１
１：同上、−400ｍＶ〜−210ｍＶの処理材、１
２：同上、−450ｍＶの処理材、１３，１４：着色
終了点電位に到達すると同時に着色液より取り出
した処理材（比較材）、ａ値、ｂ値：クロマチイ
ツクネス指数。
Fig. 1 is a potential-time curve diagram of coloring treatment, Fig. 2 is a potential-time curve diagram of coloring termination reaction according to the present invention, and Fig. 3 is a chromaticity index characteristic curve of color measurement results of treated material according to the present invention. FIG. 4 is a chromaticity index characteristic curve diagram of the color measurement results of the treated material according to the present invention. In the figure, A: Inflection point potential, B: Coloring end point potential, B-
A: Coloring potential difference, C: Coloring potential after application of external voltage, 1: Treatment material held for 2 minutes after reaching the coloring end point potential, 2: After reaching the coloring end point potential,
Potential of stainless steel relative to reference electrode -180m
Treated material held at V for 2 minutes, 3: Same as above, -200mV
Treated material, 4: Same as above, -205 mV treated material, 5 to 1
1: Same as above, -400mV to -210mV treated material, 1
2: Same as above, treated material at -450 mV, 13, 14: Treated material taken out from the colored solution at the same time as the coloring end point potential was reached (comparative material), a value, b value: chromaticity index.
Claims (1)
色水溶液中で被着色ステンレス鋼に外部電圧を印
加してカソードにすることを特徴とするステンレ
ス鋼の着色停止法。 ２ 着色水溶液中で被着色ステンレス鋼をカソー
ドとして対極間に電流を流す場合、着色水溶液中
に浸漬したPt参照電極に対して該ステンレス鋼
が−400ｍＶから−210ｍＶの電位差を生じさせる
特許請求の範囲第１項に記載のステンレス鋼の着
色停止法。 ３ 対極としてPtを用いる特許請求の範囲第１
項または第２項に記載のステンレス鋼の着色停止
法。 ４ 対極としてAgを用いる特許請求の範囲第１
項または第２項に記載のステンレス鋼の着色停止
法。 ５ 対極としてPbを用いる特許請求の範囲第１
項または第２項に記載のステンレス鋼の着色停止
法。 ６ 対極としてTiを用いる特許請求の範囲第１
項または第２項に記載のステンレス鋼の着色停止
法。[Claims] 1. A method for stopping coloring of stainless steel, which comprises applying an external voltage to the stainless steel to be colored in a stainless steel coloring aqueous solution consisting of chromic acid and sulfuric acid to make it a cathode. 2. Claims that when a current is passed between counter electrodes in a colored aqueous solution using the stainless steel to be colored as a cathode, the stainless steel generates a potential difference of -400 mV to -210 mV with respect to a Pt reference electrode immersed in the colored aqueous solution. The method for stopping coloring of stainless steel as described in item 1. 3 Claim 1 using Pt as the counter electrode
A method for stopping staining of stainless steel according to item 1 or 2. 4 Claim 1 using Ag as the counter electrode
A method for stopping staining of stainless steel according to item 1 or 2. 5 Claim 1 using Pb as a counter electrode
A method for stopping staining of stainless steel according to item 1 or 2. 6 Claim 1 using Ti as a counter electrode
A method for stopping staining of stainless steel according to item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15399381A JPH0230390B2 (en) | 1981-09-30 | 1981-09-30 | SUTENRESUKONOCHAKUSHOKUTEISHIHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15399381A JPH0230390B2 (en) | 1981-09-30 | 1981-09-30 | SUTENRESUKONOCHAKUSHOKUTEISHIHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5858298A JPS5858298A (en) | 1983-04-06 |
| JPH0230390B2 true JPH0230390B2 (en) | 1990-07-05 |
Family
ID=15574566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15399381A Expired - Lifetime JPH0230390B2 (en) | 1981-09-30 | 1981-09-30 | SUTENRESUKONOCHAKUSHOKUTEISHIHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0230390B2 (en) |
-
1981
- 1981-09-30 JP JP15399381A patent/JPH0230390B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5858298A (en) | 1983-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4026737A (en) | Method for coloring a stainless steel | |
| JPH0230390B2 (en) | SUTENRESUKONOCHAKUSHOKUTEISHIHO | |
| JPS58221283A (en) | Pretreatment of stainless steel before coloring | |
| JPH0527719B2 (en) | ||
| JPS5839237B2 (en) | Electrolytic coloring of anodized aluminum | |
| US3839096A (en) | Reproducibility of color in coloring stainless steel | |
| US3346469A (en) | Method of selectively coloring titanium bodies | |
| EP0846783A1 (en) | Method for color development of metallic titanium, and black titanium and colored titanium prepared by said method | |
| JPS58167778A (en) | Continuous coloration of stainless steel strip | |
| JPH0230391B2 (en) | SUTENRESUKONOCHAKUSHOKUHANNOTEISHIHOHO | |
| JPS5658990A (en) | Surface treating method of titanium and titanium alloy | |
| JPS63199894A (en) | Method for electrolytically developing color on titanium and titanium alloy | |
| SU729281A1 (en) | Method of light-blue chemical dyeing of copper surface | |
| JP3886557B2 (en) | Bright annealed stainless steel sheet for coloring and method for producing the same | |
| JPS6234831B2 (en) | ||
| JPH07252690A (en) | Stainless steel for coloring and coloring method of stainless steel | |
| SU1216257A1 (en) | Electrolyte for anode painting of copper | |
| JPS5928574A (en) | Coloration pretreatment of stainless steel | |
| KR910003037B1 (en) | Oxide color treatment for a stainless steel | |
| JPH02107798A (en) | Method for coloring stainless steel | |
| JPS6153440B2 (en) | ||
| SU815081A1 (en) | Method of chemical colouring of stainless steel | |
| SU651054A1 (en) | Method of anodizing titanium and its alloys | |
| JPS583040B2 (en) | Stainless Steel | |
| SU114163A2 (en) | The method of decorative finishing products |