JPH0121873B2 - - Google Patents
Info
- Publication number
- JPH0121873B2 JPH0121873B2 JP57136879A JP13687982A JPH0121873B2 JP H0121873 B2 JPH0121873 B2 JP H0121873B2 JP 57136879 A JP57136879 A JP 57136879A JP 13687982 A JP13687982 A JP 13687982A JP H0121873 B2 JPH0121873 B2 JP H0121873B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- coloring
- color tone
- present
- current density
- 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
Links
- 238000000034 method Methods 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 238000004040 coloring Methods 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Description
本発明はクロム酸−硫酸混合溶液を使用するス
テンレス鋼の着色処理における色調の再現性を高
めることができる前処理方法に関する。
クロム酸−硫酸混合溶液による発色を利用して
ステンレス鋼を着色する方法として、ステンレス
鋼を前記溶液中に浸漬してその経時変化による色
調を自然電位により把握して種々の色調に着色す
る方法がある。この方法はステンレス鋼を70〜90
℃のクロム酸−硫酸混合溶液に浸漬した場合、色
調が時間の経過とともにブルー、ゴールド、レツ
ドおよびグリーンと順次変化し、またそれに伴つ
て自然電位が変化する点を利用して、その自然電
位により色調調整を行うもので、原理的には自然
電位が一定になつた時点でステンレス鋼を混合溶
液より引上げて発色を中止すれば一定の色調に着
色できる点を特徴としている。このため従来この
方法は着色後さらに皮膜硬化処理を施すことによ
り建築用内外装材、浴槽エプロン、各種化粧板等
美感を必要とする用途の着色ステンレス鋼板の製
造に広く利用されている。
しかしながらこの方法の場合自然電位を精度よ
く管理しても鋼の成分差や製造差が色調に微妙な
差となつて現れ、その色調の再現性は従来必ずし
も充分でなく、また色調の彩度まで制御できるも
のではなかつた。
このような問題を解決する方法として従来着色
処理前にステンレス鋼を10％リン酸溶液中で電解
処理する方法が提案されている。しかしながらこ
の前処理方法の場合電解液として廃液が公害上問
題となる高濃度リン酸溶液を使用し、電解も高電
流密度（10A／ｄm2以上）で長時間（４分以上）
行わなければならないため連続化できず、製造コ
ストは高くつくものであつた。また現れる自然電
位曲線もなだらかな上昇曲線で、着色開始点が明
確に現れないため色調管理がむずかしいものであ
つた。
本発明はステンレス鋼の成分差や製造差に関係
なく、その表面性状を均一にし、しかも上記のよ
うな問題のないステンレス鋼の着色前処理方法を
提供するものである。
本発明の前処理方法はステンレス鋼を1.0〜
8.0wt％の硝酸水溶液中で液温20〜80℃、電流密
度0.5〜3.0A／ｄm2でステンレス鋼を陽極として
15〜60秒間電解処理することによりステンレス鋼
の表層をわずかに溶解して、ステンレス鋼表面に
形成されていた酸化皮膜の除去と、新たな緻密不
働態皮膜の形成とを行い、これにより着色処理の
際の色調の再現性および彩度の制御を可能にした
ものである。
電解条件は硝酸濃度が1.0wt％未満、液温が20
℃未満、電流密度が0.5A／ｄm2未満であると電
解反応が遅くなるため電解時間が長くなり、工業
的には不適当となる。一方硝酸濃度が8.0wt％を
超え、また液温および電流密度もそれぞれ80℃お
よび3.0A／ｄm2を超えると電解反応が速くなつ
て鋼素地まで溶解し、かつ溶出金属による電解液
の老化も早くなる。
添付図面はSUS304HL仕上材を従来法と本発
明法で前処理した後、それらに着色処理を施した
場合の自然電位曲線を示したもので、従来法の場
合着色開始点の現れないなだらかな上昇曲線とな
るが、本発明法の場合一旦ピークを形成した後再
び上昇する曲線となつて、着色開始点がピークの
立下りより上昇に移る点に現れる。従つて本発明
法によれば色調の管理や制御は容易になり、色調
の再現性が向上する。
第１表はSUS304BA仕上材を本発明法、従来
法で前処理した後CrO32.5M／ｌ、H2SO45M／
、液温80℃、自然電位23ｍＶで着色処理したも
のの色調再現性を示したもので、本発明法により
前処理を施したものは色差計による色差ΔEが0.3
以下であり、再現性に優れている。このような色
調の再現性は本発明法を適用すればフエライト系
ステンレス鋼など他の鋼種および仕上材について
も得られるものである。
The present invention relates to a pretreatment method that can improve the reproducibility of color tone in coloring treatment of stainless steel using a mixed solution of chromic acid and sulfuric acid. As a method of coloring stainless steel using the coloring produced by a mixed solution of chromic acid and sulfuric acid, there is a method of immersing stainless steel in the solution and coloring it into various tones by determining the color tone due to the change over time using natural potential. be. This method uses stainless steel from 70 to 90
When immersed in a chromic acid-sulfuric acid mixed solution at It adjusts the color tone, and is characterized in that it can be colored to a fixed color tone by lifting the stainless steel from the mixed solution and stopping color development once the natural potential becomes constant. For this reason, this method has conventionally been widely used to produce colored stainless steel sheets for applications that require aesthetic appeal, such as interior and exterior materials for buildings, bathtub aprons, and various decorative laminates, by further subjecting the steel to a film hardening treatment after coloring. However, with this method, even if the self-potential is precisely controlled, differences in the composition and manufacturing of the steel will result in subtle differences in color tone, and the reproducibility of the color tone has not always been sufficient, and the saturation of the color tone It wasn't something I could control. As a method to solve these problems, a method has been proposed in which stainless steel is electrolytically treated in a 10% phosphoric acid solution before coloring. However, in this pretreatment method, a highly concentrated phosphoric acid solution is used as the electrolyte, and the waste liquid is a pollution problem, and the electrolysis is performed at a high current density (10 A/dm 2 or more) for a long time (4 minutes or more).
Since this process had to be repeated, it could not be made continuous, and the manufacturing cost was high. Furthermore, the self-potential curve that appears is a gentle rising curve, and the coloring start point does not clearly appear, making color tone control difficult. The present invention provides a method for pre-coloring stainless steel, which makes the surface properties of stainless steel uniform regardless of differences in its components and production, and which is free from the above-mentioned problems. The pretreatment method of the present invention can treat stainless steel from 1.0 to
In an 8.0wt% nitric acid aqueous solution at a liquid temperature of 20 to 80℃ and a current density of 0.5 to 3.0A/ dm2 , stainless steel was used as an anode.
Electrolytic treatment for 15 to 60 seconds slightly dissolves the surface layer of stainless steel, removes the oxide film that had formed on the stainless steel surface, and forms a new dense passive film, which results in coloring. This makes it possible to control color tone reproducibility and saturation during printing. Electrolysis conditions are nitric acid concentration less than 1.0wt%, liquid temperature 20
If the current density is less than 0.5 A/dm 2 , the electrolytic reaction will be slow and the electrolytic time will be long, making it unsuitable for industrial use. On the other hand, if the nitric acid concentration exceeds 8.0wt%, and the liquid temperature and current density also exceed 80℃ and 3.0A/ dm2 , respectively, the electrolytic reaction becomes faster and even the steel base is dissolved, and the electrolyte deteriorates due to eluted metal. It gets faster. The attached drawing shows the natural potential curve when SUS304HL finishing material is pretreated by the conventional method and the method of the present invention and then subjected to coloring treatment.In the case of the conventional method, there is a gentle rise without a coloring start point. However, in the case of the method of the present invention, the curve is a curve that once forms a peak and then rises again, and the coloring start point appears at the point where the peak shifts from falling to rising. Therefore, according to the method of the present invention, the management and control of color tone becomes easy, and the reproducibility of color tone is improved. Table 1 shows the results of SUS304BA finishing material after pretreatment using the method of the present invention and the conventional method: CrO 3 2.5M/l, H 2 SO 4 5M/l
, which shows the color tone reproducibility of a product that was colored at a liquid temperature of 80°C and a natural potential of 23 mV, and the color difference ΔE measured by a color difference meter was 0.3 for the product pretreated by the method of the present invention.
The reproducibility is excellent. Such color tone reproducibility can also be obtained for other steel types and finishing materials, such as ferritic stainless steel, by applying the method of the present invention.
【表】
以上の如く、本発明の前処理法は電解液として
硝酸を使用し、かつその濃度はリン酸の場合より
低濃度であるので、その廃液処理はリン酸より容
易であるとともに処理後の液はリン酸を含まない
ので放出しても公害上問題はない。また電解条件
は低電流密度、短時間電解であるので、ストリツ
プによる連続化が可能であり、かつ自然電位曲線
にも着色開始点が現れ、色調管理も容易となるの
で、歩留も向上し、製造コストが低減する。[Table] As described above, the pretreatment method of the present invention uses nitric acid as the electrolyte, and its concentration is lower than that of phosphoric acid, so the waste liquid treatment is easier than with phosphoric acid, and the treatment after treatment is Since the liquid does not contain phosphoric acid, there is no pollution problem even if it is released. In addition, since the electrolysis conditions are low current density and short time electrolysis, continuous striping is possible, and the coloring start point appears on the self-potential curve, making color tone control easier, improving yield. Manufacturing costs are reduced.
添付図面は本発明法と従来法で前処理した
SUS304HL仕上材の着色処理における自然電位
曲線を示すものである。
The attached drawings are pre-treated using the method of the present invention and the conventional method.
This figure shows the natural potential curve in the coloring treatment of SUS304HL finishing material.
Claims (1)
色処理するにあたり、あらかじめ1.0〜8.0wt％の
硝酸水溶液中で液温20〜80℃、電流密度0.5〜
3.0A／ｄm2でステンレス鋼を陽極として15〜60
秒間電解処理し、表面層をわずかに溶解して均一
な不動態皮膜を形成することを特徴とするステン
レス鋼の着色前処理方法。1. When coloring stainless steel with a mixed solution of chromic acid and sulfuric acid, pre-incubate in a 1.0 to 8.0 wt% nitric acid aqueous solution at a liquid temperature of 20 to 80°C and a current density of 0.5 to
15-60 using stainless steel as anode at 3.0A/ dm2
A pre-coloring method for stainless steel characterized by electrolytic treatment for seconds to slightly dissolve the surface layer and form a uniform passive film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13687982A JPS5928574A (en) | 1982-08-06 | 1982-08-06 | Coloration pretreatment of stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13687982A JPS5928574A (en) | 1982-08-06 | 1982-08-06 | Coloration pretreatment of stainless steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5928574A JPS5928574A (en) | 1984-02-15 |
| JPH0121873B2 true JPH0121873B2 (en) | 1989-04-24 |
Family
ID=15185668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13687982A Granted JPS5928574A (en) | 1982-08-06 | 1982-08-06 | Coloration pretreatment of stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5928574A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898493A (en) * | 2014-04-10 | 2014-07-02 | 哈尔滨飞机工业集团有限责任公司 | Brush plating cadmium passivating solution as well as preparation method and passivating method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63248802A (en) * | 1987-04-03 | 1988-10-17 | Ube Ind Ltd | Polymerization of alpha-olefin using preactivated catalyst |
| KR100761903B1 (en) | 2006-05-01 | 2007-09-28 | 김영희 | Method for manufacturing high corrosion-resistant color steel materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147545A (en) * | 1974-10-23 | 1976-04-23 | Nippon Steel Corp | Sutenresukono chakushokumaeshorihoho |
| JPS51120939A (en) * | 1975-04-17 | 1976-10-22 | Nippon Steel Corp | Process for coloring stainless steel |
-
1982
- 1982-08-06 JP JP13687982A patent/JPS5928574A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147545A (en) * | 1974-10-23 | 1976-04-23 | Nippon Steel Corp | Sutenresukono chakushokumaeshorihoho |
| JPS51120939A (en) * | 1975-04-17 | 1976-10-22 | Nippon Steel Corp | Process for coloring stainless steel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103898493A (en) * | 2014-04-10 | 2014-07-02 | 哈尔滨飞机工业集团有限责任公司 | Brush plating cadmium passivating solution as well as preparation method and passivating method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5928574A (en) | 1984-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0121873B2 (en) | ||
| US2888391A (en) | Process for coating metal | |
| ES419556A2 (en) | Method of increasing the hardness of a film formed on the surface of an alloy. (Machine-translation by Google Translate, not legally binding) | |
| ES8205885A2 (en) | Process for the electrolytic coloring of aluminum or aluminum alloys | |
| JPS5827997A (en) | Pretreatment of stainless steel for color formation | |
| US1946150A (en) | Coating of aluminum | |
| JPS5729595A (en) | Formation of colored film of aluminum | |
| JPS58221283A (en) | Pretreatment of stainless steel before coloring | |
| US2855350A (en) | Process for electrolytically producing oxide coating on aluminum and aluminum alloys | |
| US3891517A (en) | Process for electrolytic coloring of aluminum cr aluminum alloy articles | |
| JPS5757893A (en) | Manufacture of electrolytically chromate treated steel plate causing less deterioration in bonding strength due to aging | |
| JPS5651593A (en) | Surface treating method of aluminum | |
| JPS5917200B2 (en) | How to remove colored film from stainless steel | |
| JPS5735698A (en) | Production of chromate film steel plate for vessel of superior weldability and corrosion resistance after painting | |
| JPS5524947A (en) | Formation of nontransparent anodic oxide film in aluminium-clad material | |
| JPS5558395A (en) | Production of tinfree steel | |
| JPS5521562A (en) | Method of forming grain pattern to aluminium or aluminium alloy material | |
| JPS5615396A (en) | Manufacture of alminum support substance for lithographic plate | |
| JPS56144195A (en) | Manufacture of supporter for lithographic plate | |
| JPS6029489A (en) | Surface treatment of aluminum alloy for patterning | |
| JPS5562196A (en) | Surface treating method of aluminum or aluminum alloy | |
| JPS5616697A (en) | Preparation of chromic acid treaded steel sheet having low deterioration on standing of adhesive strength | |
| JPH032394A (en) | Method for coloring austenitic stainless steel | |
| JPS607714B2 (en) | Surface treatment method for aluminum materials | |
| JPS6260891A (en) | Method for coloring stainless steel material |