JPS5837192A - Post-treatment for non-plated surface of steel plate electroplated with zinc on one side - Google Patents
Post-treatment for non-plated surface of steel plate electroplated with zinc on one sideInfo
- Publication number
- JPS5837192A JPS5837192A JP13660881A JP13660881A JPS5837192A JP S5837192 A JPS5837192 A JP S5837192A JP 13660881 A JP13660881 A JP 13660881A JP 13660881 A JP13660881 A JP 13660881A JP S5837192 A JPS5837192 A JP S5837192A
- Authority
- JP
- Japan
- Prior art keywords
- plated surface
- phosphate
- plated
- iron
- zinc
- 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
Links
Abstract
Description
【発明の詳細な説明】
本発明は片面電気亜鉛メッキ鋼板の非メッキ面に生成す
る変色物質の除去を該非メッキ面のリン酸塩処理性を改
善させる後処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a post-treatment method for removing discoloration substances generated on the non-plated surface of a single-sided electrogalvanized steel sheet and improving the phosphatability of the non-plated surface.
片面亜鉛メッキ鋼板は自動車用外板材として車体寿命を
伸ばすため主に用いられる。従来の両面亜鉛メッキ鋼板
は、塗装後の性能、特に耐ブリスター性が悪く、塗装劣
化が早期に起こる。この様に亜鉛メッキ面は塗装劣化を
起こすことから、自動車の外板には、塗装を施こす外面
をメッキをしない面として上記の塗装劣化を防止し、内
面を亜鉛メッキ面として鋼板を防錆する片面亜鉛メッキ
鋼板が用いられている。Single-sided galvanized steel sheets are mainly used as exterior panel materials for automobiles to extend the life of the vehicle body. Conventional double-sided galvanized steel sheets have poor performance after painting, especially blister resistance, and paint deterioration occurs quickly. As described above, galvanized surfaces cause paint deterioration, so the exterior panels of automobiles are coated with a non-plated surface to prevent the aforementioned paint deterioration, and the inner surface is galvanized to prevent rust. Single-sided galvanized steel sheet is used.
一方、メッキ面の耐食性をより向上させるために、厚メ
ッキが求められる傾向にある。電気メッキではメッキ厚
みが厚いほど大きな通電量が必要となる。従って、連続
メツキラインで厚メッキの１鋼板を製造する場合、メツ
キラインの整流器の電気容量から、メッキ厚みが厚いほ
どライン速度を低下させる必要が生じる。電気メツキ液
には電気的に安定なところから、硫酸水溶液が主として
用いられているが、この様に低速で電気メッキをする場
合にはメッキしない面（以下非メッキ面又は鉄面という
〕がメッキ液中で複雑な酸化物を鉄面上に形成し茶色や
黒褐色に変色する・（以下黒変等いう）０これらの変色
は片面亜鉛メッキ鋼板の非メッキ面の外観を著しく損う
のみならず鉄面のリン酸塩処理性を損い、塗装後の塗装
性能を劣化させる。On the other hand, there is a tendency for thick plating to be required in order to further improve the corrosion resistance of the plated surface. In electroplating, the thicker the plating, the greater the amount of current required. Therefore, when producing one thickly plated steel plate on a continuous plating line, it becomes necessary to reduce the line speed as the plating thickness increases, due to the electric capacity of the rectifier of the plating line. Sulfuric acid aqueous solution is mainly used as the electroplating solution because it is electrically stable. However, when electroplating is performed at such low speed, the unplated surface (hereinafter referred to as non-plated surface or iron surface) is plated. In the liquid, complex oxides are formed on the iron surface, causing it to discolor to brown or blackish brown. It impairs the phosphate treatment properties of the surface and deteriorates the coating performance after painting.
従来、この様な問題点を解決するために、（１）特開昭
５３−１２２６３１．特開昭５３−１２２６３２の非メ
ッキ面に合成樹脂シートを被着してメッキ液と接触をな
くす方法。Conventionally, in order to solve such problems, (1) Japanese Patent Application Laid-Open No. 53-122631. JP-A-53-122632 discloses a method of applying a synthetic resin sheet to a non-plated surface to eliminate contact with a plating solution.
（２）特公昭５５−４６４７０の非メッキ面を陰極、陽
極と繰り返して通電を行ない非メッキ面を保護する方法
などがあった。(2) Japanese Patent Publication No. 55-46470 proposed a method of protecting the non-plated surface by repeatedly applying electricity to the non-plated surface as a cathode and an anode.
前記第（１）の方法は従来メツキラインの大巾な改造を
必要とすること、またメツキラインの各種ロー”ルと接
触する合成樹脂シートが破損しゃすく、非メッキ面と合
成樹脂シートの気密性を完全に保つことが難しいなどの
問題点があった。Method (1) above requires extensive modification of the conventional mesh line, and the synthetic resin sheet that comes into contact with the various rolls of the mesh line is likely to be damaged, making it difficult to maintain the airtightness between the non-plated surface and the synthetic resin sheet. There were problems such as difficulty in maintaining it perfectly.
第（２）の方法は黒変防止に有効と思われるが、鉄面が
陰・陽画極性を受けるため、鉄面の従来あったリン酸塩
処理性が良好である表面酸化皮膜層が変質してリン酸塩
処理性を劣化させる。また、各電解槽内の電流分布は電
極消耗の不均一や槽内流速の不均一などで、陰極時にメ
ッキされたメッキ層が陽極時に陰極時と同じ電気量を流
しても均一に溶解するのは困難であり、メッキ層が一部
残存したり鉄面の溶解があるなど、完全な鉄面の保護が
出来ない々どの問題点があった。Method (2) seems to be effective in preventing blackening, but since the iron surface is subjected to negative and positive polarization, the surface oxide film layer on the iron surface, which has good phosphate treatment properties, may deteriorate. and deteriorates phosphate treatment properties. In addition, the current distribution in each electrolytic cell is due to uneven electrode consumption and uneven flow velocity in the tank, so that the plating layer plated at the cathode will not dissolve uniformly even if the same amount of electricity is passed at the anode as at the cathode. It is difficult to protect the iron surface completely, and there are problems such as parts of the plating layer remaining or melting of the iron surface.
そこで本発明者等は、従来の電気メツキ設備をそのまま
用い、鉄面の変色物質を工業的に容易にかつメッキ面の
損失及び品質を劣化させないで除去し・鉄面の外観及び
リン酸塩処理性能を改善することを試みた。Therefore, the inventors of the present invention have developed a method for removing discoloration substances from iron surfaces industrially and easily without deteriorating the quality or loss of the plated surface by using conventional electroplating equipment as is. Attempted to improve performance.
その結果、疏酸酸性水溶液中で鋼板に片面電気亜鉛メッ
キを行なった後、非メッキ面を全リン酸濃度が０．０５
モル／１．水素イオン濃度（以下ＰＨとする）４以上７
未満の溶液中において陽極電流密度２ Ａ ／ ａ♂以
上で電解処理することにより、非メッキ面の黒変を除去
させると同時に○、ｏ５２７ｄ以下のリン酸鉄を非メツ
キ面上に生成させるととによりリン酸塩処理性が改善で
きることを見出した。以下、本発明の各条件について述
べる。As a result, after electrogalvanizing a steel plate on one side in a sulfuric acid aqueous solution, the total phosphoric acid concentration on the non-plated side was 0.05.
Mol/1. Hydrogen ion concentration (hereinafter referred to as PH) 4 or more 7
By performing electrolytic treatment at an anode current density of 2 A/a♂ or more in a solution of less than It has been found that phosphate treatment properties can be improved by Each condition of the present invention will be described below.
本発明法において極性は陽極性で黒変の電解除去が可能
であり、陰極性では黒変の除去は困難である。In the method of the present invention, when the polarity is anodic, it is possible to electrolytically remove black discoloration, whereas when the polarity is cathodic, it is difficult to remove black discoloration.
電流密度は２Ａ／ｄｎｌ’以上で黒変の除去が出来るが
、２Ａ／ｄｒ１１″未満では黒変の除去が困難となると
同時にリン酸鉄の生成量が小さくなりリン酸塩処理性の
改善には、長時間を要するので２ Ａ ／ｄｒｒ１′以
上が必要である。電解電圧の上昇による電力ロスを考慮
すると１００Ａ／ａｎ？以下が望ましい。If the current density is 2A/dnl' or higher, black discoloration can be removed, but if it is less than 2A/dnl', it becomes difficult to remove black discoloration, and at the same time, the amount of iron phosphate produced is small, making it difficult to improve phosphate treatment properties. Since it takes a long time, 2 A/drr1' or more is required. Considering power loss due to increase in electrolytic voltage, 100 A/drr1' or less is desirable.
ＰＨについては、ＰＨ７以上では黒変の除去は困難であ
り、ＰＨ４未満では鋼板の溶解が増加してリン酸鉄の生
成を阻害するためリン酸塩処理性の向上は望めない。そ
とでＰＨは４以上７未満の範囲とした。Regarding the pH, if the pH is 7 or more, it is difficult to remove black discoloration, and if the pH is less than 4, dissolution of the steel sheet increases and the production of iron phosphate is inhibited, so no improvement in phosphating properties can be expected. On the other hand, the pH was set in a range of 4 or more and less than 7.
電解液成分については、リン酸イオンを含まない中性塩
電解液２例えば硫酸ナトリウム、塩化ナト、リウム。Regarding the electrolyte components, a neutral salt electrolyte 2 containing no phosphate ions, such as sodium sulfate, sodium chloride, and lithium.
フッ化ナトリウムなどでも上記ＰＨ範囲内で黒変の除去
は可能であるが・リン酸塩処理性の改善効果がなく、ま
た酸成分である硫酸、リン酸、硝酸、過塩素酸なども黒
変の除去は可能であるが、リン酸塩処理性の改善効果が
ない。Although it is possible to remove black discoloration with sodium fluoride within the above pH range, it does not have the effect of improving phosphate treatment properties, and acid components such as sulfuric acid, phosphoric acid, nitric acid, and perchloric acid can also remove black discoloration. can be removed, but there is no improvement in phosphate treatment properties.
リン酸塩の濃度は全リン酸濃度として０．０５モル／を
以上で黒変の除去とリン酸塩処理性が改善されるが０．
０５モル／を未満になるとリン酸鉄の生成が困難となシ
リン酸塩処理性の改善効果が小さくなる。また上限はリ
ン酸塩の溶解度以下が望ましい。リン酸塩としては、す
／酸ナトリウムが適当であり、リン酸又は水酸化ナトリ
ウム溶液を用いてＰＨを調整するのが望ましい。When the total phosphoric acid concentration is 0.05 mol/or more, the removal of black discoloration and the phosphate treatment properties are improved, but the phosphate concentration is 0.05 mol/or more.
When the amount is less than 0.05 mol/mol, it becomes difficult to produce iron phosphate, and the effect of improving syphosphate treatment properties becomes small. Further, the upper limit is preferably equal to or lower than the solubility of the phosphate. As the phosphate, sodium chloride is suitable, and it is desirable to adjust the pH using phosphoric acid or a sodium hydroxide solution.
電解液の電導度を上げるために、Ｎａ２Ｓ ０４ 、
（ＮＨ４）２ｓｏ４等の強電解質塩を添加しても良いが
、リン酸塩処理性の改善効果を得るためには、全リン酸
濃度の％当量以下のアニオン濃度が望ましい。但し塩素
イオンなどのハロゲンイオンの濃度は０．０１モル／を
以下が必要で、それを越えると電解処理後、鉄面に黄変
が生じて、リン酸塩処理性が悪くなる。In order to increase the conductivity of the electrolyte, Na2S 04 ,
A strong electrolyte salt such as (NH4)2so4 may be added, but in order to obtain the effect of improving phosphate treatment properties, the anion concentration is preferably less than % equivalent of the total phosphoric acid concentration. However, the concentration of halogen ions such as chloride ions must be 0.01 mol/or less; if it exceeds this, yellowing will occur on the iron surface after electrolytic treatment, and the phosphate treatment properties will deteriorate.
リン酸鉄の生成量がｏ、ｏ５ｙ／、／を越えると・非メ
ツキ面上の酸化皮膜量が増加することでリン酸塩処理性
が悪くなる。そこで本発明法では０．０５Ｖ／ぜ以下と
する。When the amount of iron phosphate produced exceeds o, o5y/, /, the amount of oxide film on the non-plated surface increases, resulting in poor phosphate treatment properties. Therefore, in the method of the present invention, the voltage is set to 0.05 V/ze or less.
本発明の黒変除去およびリン酸塩処理性が向上する理由
は、明確でないが次の通りであ丸とみられる。The reason why the black discoloration removal and phosphate treatment properties of the present invention are improved is not clear, but it is generally believed to be as follows.
本発明における鉄面の電解時の電位は、甘木照合電極を
基準として約１．５ｖ以上となシ、鉄面は過不動態域と
なる。In the present invention, the potential during electrolysis of the iron surface is about 1.5 V or more with respect to the Amagi reference electrode, and the iron surface is in a hyperpassive region.
過不動態域での電極反応は次の式で示される。The electrode reaction in the hyperpassive region is expressed by the following equation.
＋
２０Ｈ−＋０２＋２Ｈ＋２ｅ ・ ・・ −−（
］Ｊ 。+ 20H-+02+2H+2e ・ ・・ −−(
]J.
Ｆｅ →Ｆθ３＋＋３０ ・ ・ ・ ・
・（２）２Ｆｅ’＋３Ｈ２０→γＦｅ２Ｏ３＋６Ｈ＋＋
６ｅ Ｈ・（３）。 −３
Ｆｅ ＋ＰＯ４→ＦθＰＯ４・・・・−（３１’酸素発
生反応式（１）が主反応で、地鉄溶解反応式（２）と皮
膜形成反応式（３）が同時に起こる、リン酸イオンが存
在すると式（３）は式（３′）になる。Fe →Fθ3++30 ・ ・ ・ ・
・(2) 2Fe'+3H20→γFe2O3+6H++
6e H. (3). -3 Fe +PO4→FθPO4...-(31' Oxygen generation reaction formula (1) is the main reaction, base metal dissolution reaction formula (2) and film formation reaction formula (3) occur simultaneously, phosphate ion If it exists, equation (3) becomes equation (3').
この過不動態域での黒変除去理由は、
（１）わずかな地鉄溶解により黒変皮膜が剥離すると共
に酸素ガス発生によるメカニカル作用によって一層黒変
皮膜除去が促進される。The reasons for removing black discoloration in this overpassive region are as follows: (1) A slight dissolution of the base metal causes the black discoloration film to peel off, and the removal of the black discoloration film is further promoted by the mechanical action of oxygen gas generation.
（２）陽極界面は式（１）により水素イオンが多くなり
ＰＨが低下して黒変皮膜が溶解する。(2) According to formula (1), hydrogen ions increase at the anode interface, the pH decreases, and the blackened film dissolves.
（３）アニオン（本発明の場合リン酸イオンフの吸着に
よって表面張力が低下し、黒変皮膜がコロイド化される
と共に高電位におかれ電気歪を受けて黒変皮膜が破壊す
ること等によるものとみられ、以上の反応が個々に・ま
たは複合して黒変が除去される。次にリン酸塩処理性の
向上について述べる。(3) Anions (in the case of the present invention, the surface tension decreases due to the adsorption of phosphate ions, the blackened film is colloidized, and the blackened film is destroyed by being subjected to electrostriction when placed at a high potential, etc.) It appears that the above reactions individually or in combination remove black discoloration.Next, we will discuss the improvement of phosphate treatment properties.
焼鈍過程力どで形成された鋼板表面の酸化皮膜を酸洗な
どにより除去した鉄面ば、非常に安定した酸化皮膜が形
成されやすくなシ、リン酸塩処理性が悪くなる。本発明
は過不動態域での電解であり、リン酸イオンを含有する
ところから、式（３）の皮膜形成反応が起きＦ ｅ Ｐ
０４皮膜が形成さ些て、これがリン酸塩処理時の核と
なり適正なリン酸塩結晶を形成させる。If the oxide film formed on the surface of the steel sheet by the annealing process is removed by pickling or the like, a very stable oxide film is likely to be formed on the steel surface, and the phosphate treatment properties will be poor. The present invention is electrolysis in a hyperpassive region, and since it contains phosphate ions, the film forming reaction of formula (3) occurs, F e P
Once the 04 film is formed, it becomes a nucleus during phosphate treatment and forms proper phosphate crystals.
次に本発明の詳細を実施例に基づいて説明する。Next, details of the present invention will be explained based on examples.
第１図は従来技術による片面電気亜鉛メッキ装置の設備
配置図を示し、アンコイラーユから捲戻されるストリッ
プは脱脂槽４で脱脂され、水洗槽５で水洗され、次に酸
洗槽６で酸洗、水洗槽７で水洗後、電気亜鉛メッキ槽８
で片面メッキされ、水洗槽９で水洗、乾燥機ｌＯ″′Ｃ
乾燥されリコイラー１２で捲取られる。なお図中２．１
１はシャー、３は溶接機である。このようにして、第１
図に示す連続電気亜鉛メッキ装置において、帯鋼（巾１
２００、、板厚０−８ ｍｍ ）をラインスピード４０
ｍ／胴で片面にｓｏｆ／ｒｎ”メッキしたところ、メッ
キしない鉄面にメッキ檜出口で焦茶色の変色が生じた。FIG. 1 shows an equipment layout diagram of a single-sided electrogalvanizing apparatus according to the prior art, in which the strip unwound from the uncoilail is degreased in a degreasing tank 4, washed with water in a washing tank 5, and then pickled in a pickling tank 6. , After washing with water in washing tank 7, electrogalvanizing tank 8
plated on one side, washed in washing tank 9, and dried in lO'''C.
It is dried and rolled up by a recoiler 12. In addition, 2.1 in the figure
1 is a shear, and 3 is a welding machine. In this way, the first
In the continuous electrogalvanizing equipment shown in the figure, a strip steel (width 1
200, plate thickness 0-8 mm) at line speed 40
When plating one side of the m/barrel with "sof/rn", dark brown discoloration occurred on the unplated iron surface at the outlet of the plated cypress.
尚、メッキ液はＺｎＳＯ４・７）Ｔ２ＯとＨ２ＢＯ３お
よびＮａ２ＳＯ４を水に溶解したものを使用している。The plating solution used is a solution of ZnSO4.7) T2O, H2BO3, and Na2SO4 in water.
第２図は本発明による片面電気亜鉛メッキの設備配置で
ある。従来技術による片面電気亜鉛メッキ装置の設備配
置図、第１図の水洗槽９のあとに電解槽１３．水洗槽１
４が設けられている。FIG. 2 shows the equipment layout for single-sided electrogalvanizing according to the present invention. An equipment layout diagram of a single-sided electrogalvanizing apparatus according to the prior art, in which an electrolytic tank 13 is installed after the washing tank 9 in FIG. Washing tank 1
4 are provided.
電解槽１３の１例の詳細図を第３図に示す。A detailed diagram of one example of the electrolytic cell 13 is shown in FIG.
電極１５を鉄面に対置させる。１６は押えロール、１７
は通電ロールである。The electrode 15 is placed opposite to the iron surface. 16 is a presser roll, 17
is an energized roll.
次表に本発明の実施例および比較例の結果を示す。メッ
キ液はＺｎＳＯ４・７Ｈ２０２００２／ｌ、Ｈ２ＳＯ４
２５ ｔ ／ ｌ ＋ Ｎ ａ２ Ｓ ０４ １００
ｔ／ Ｚ ｒ Ｐ Ｈ１−０＋温度６０℃である。The following table shows the results of Examples of the present invention and Comparative Examples. Plating solution is ZnSO4・7H202002/l, H2SO4
25 t/l + N a2 S 04 100
t/ZrPH1-0+Temperature is 60°C.
電解処理後の鉄面の外観評価は、◎金属色、○やや黄色
味のある金属色、Δ黒変が一部残る。×黒変が残る、と
した°。Appearance evaluation of the iron surface after electrolytic treatment was as follows: ◎ Metallic color, ○ Slightly yellowish metallic color, ∆ black discoloration partially remaining. ×Black discoloration remains.°
リン酸塩の処理条件は、日本バーカーライジング株制の
薬剤を用いた。ファインクリーナー−４３４９の脱脂剤
、濃度２ｏ２／ｌ、処理温度５−５℃、処理時間１２０
秒、スプレー脱脂後、水洗した後ボンデライ）３１１Ｂ
を用い遊離酸度ｏ、５〜０．７ポイント、全酸度１４〜
１５ポイント、促進剤濃度１．５〜２．０ポイントに調
整した液を用い、１２０秒間スプレー処理した後、リン
酸塩結晶の付着量及び結晶粒径を測定した。For the phosphate treatment conditions, a chemical from the Japan Barker Rising strain system was used. Fine Cleaner-4349 degreasing agent, concentration 2o2/l, treatment temperature 5-5℃, treatment time 120
Second, after spray degreasing, after washing with water Bonderai) 311B
using free acidity o, 5 to 0.7 points, total acidity 14 to
After spraying for 120 seconds using a solution adjusted to 15 points and a promoter concentration of 1.5 to 2.0 points, the amount of phosphate crystals attached and the crystal grain size were measured.
表に示すようにＡは一般冷延鋼板のリン酸塩処理性を示
し、この数値になれば適正と言える。Ｂは便来の片面メ
ッキ鋼板の鉄面のリン酸塩処理性を示し・Ａと比較して
著るしく劣っている。リン酸塩以外の比較例Ｃは外観が
改善されるが、リン酸塩処理性が悪い。酸類及びＰＨが
４未満の比較例り、Ｅ、Ｆは外観は改善されるがリン酸
塩処理性は悪い。極性が陰極である比較例Ｇ、Ｈは黒変
がとれない。比較例Ｐはリン酸イオン濃度に対し当量超
の硫酸イオン濃度がありリン酸塩処理性を若干悪くして
いる。比較例Ｑはリン酸イオン濃度が低くリン酸塩処理
性が劣化する。比較例１Ｒは電流密度が低く比較例Ｓは
ＰＨが高く外観、リン酸塩処理性とも悪い。As shown in the table, A indicates the phosphate treatment property of general cold-rolled steel sheets, and it can be said that this value is appropriate. B shows the phosphate treatment properties of the iron surface of conventional single-sided plated steel sheets, and is significantly inferior to A. Comparative Example C other than phosphate has improved appearance but poor phosphate treatment properties. Comparative examples with acids and pH less than 4, E and F, have improved appearance but poor phosphate treatment properties. In Comparative Examples G and H, in which the polarity is cathode, the black discoloration cannot be removed. In Comparative Example P, the sulfate ion concentration exceeds the equivalent of the phosphate ion concentration, which slightly deteriorates the phosphate treatment properties. Comparative Example Q has a low phosphate ion concentration and deteriorates phosphate treatment properties. Comparative Example 1R has a low current density, and Comparative Example S has a high pH and is poor in appearance and phosphate treatment properties.
本発明例Ｉ、Ｊ、に、Ｌ、Ｍ、Ｎ、Ｏは比較例Ｂ、Ｃ，
Ｄ、Ｅ、Ｆ、Ｇ、Ｈ，Ｐ、Ｑ、Ｒ，Ｓに比較し良好な外
鉄とリン酸塩処理性を示している。Invention examples I, J, L, M, N, O are comparative examples B, C,
It shows better external iron and phosphate treatability compared to D, E, F, G, H, P, Q, R, and S.
次に本発明の利点を述べる。Next, the advantages of the present invention will be described.
（１）、ＰＨが比較的高いためメッキ面の溶出が著るし
く小さく、亜鉛面の損失及び性能劣化がない。(1) Since the pH is relatively high, the elution from the plated surface is extremely small, and there is no loss of zinc surface or performance deterioration.
（２）鉄面の溶出が著るしく小さく、電解液の劣化が少
ない。(2) Elution from the iron surface is significantly small, and there is little deterioration of the electrolyte.
（３）メッキ面、鉄の溶出が少ない事から、陰極である
電極材への電析が少ない。(3) Since there is little elution of iron from the plated surface, there is little electrodeposition on the electrode material, which is the cathode.
（４）酸洗に見られる酸洗後の黄変現象がない。(4) There is no yellowing phenomenon after pickling that occurs during pickling.
（５）リン酸イオンを含む中性塩は、緩衝作用が強く、
電解によるＰＨ変化が少ない。(5) Neutral salts containing phosphate ions have a strong buffering effect,
There is little pH change due to electrolysis.
（６）電解による有毒ガスの発生がない。(6) No toxic gas is generated due to electrolysis.
本発明は硫酸酸性水溶液を用いる亜鉛系合金片面電気メ
ツキ鋼板９例えばＺｎ−ＩＪｉ系、ｚｎ−Ｎｉ−ＣＯ系
、Ｚｎ−Ｆｅ系、 Ｚｎ−Ｎ１−Ｆ’ｓ系、 Ｚ ｎ−
Ｎ１Ｌ−Ｆｅ−Ｃ３ｒ系などの非メッキ面への適用も可
能である。The present invention is a zinc-based alloy single-sided electroplated steel sheet 9 using a sulfuric acid acidic aqueous solution, such as Zn-IJi system, Zn-Ni-CO system, Zn-Fe system, Zn-N1-F's system, Zn-
Application to non-plated surfaces such as N1L-Fe-C3r is also possible.
第１図は通常の片面電気メツキ装置の設備配置図・
第２図及び第３図は本発明実−例装置の設備配置図であ
る。
１・・・・アンコイラ−２・・・シャー３・・・・溶接
機 ４・・・脱脂槽５・・・・水洗槽
６・・・酸洗槽７・・・・水洗槽 ８・・・
電気メツキ槽９・・・・水洗槽 １０・・乾燥
機１１・・・シャー １２・・リコイラー１３
・・・電解槽 １４・・・水洗槽１５・・・電
極 １６・・・押えロール１７・・・通電ロ
ール
出 願 人 新日本製鐵株式会社
１１！３図
手続補正書（自発）
昭和５７年１月１２日
特許庁長官 殿
Ｌ 事件の表示 昭和５６年特許願第１３６６０８号２
発明の名称 片面電気亜鉛メッキ鋼板の非メッキ面の
後処理方法
３ 補正をする者
事件との関係 特許出願人
住 所 東京都千代田区大手町２丁目６番３号名 称
（６６５）新日本製鐵株式会社代表者 武 １）
豊
４代理人〒１０３ 置 ２４１−０４４ｉ住 所 東
京都中央区日本橋本町１丁目１４番２号明細書の発明の
名称、特許請求の範囲、発明の詳細な説明、及び図面の
簡単な説明の欄
補 正 書
Ｌ 発明の名称を次の通シ補正する。
片面亜鉛系電気メツキ鋼板の非メッキ面の後処理方法
２、特許請求の範囲を別紙の通り補正する。
３ 明細書１頁１５行目
［片面電気亜鉛メッキ］とあるのを
「片面亜負系電気メッキ」に訂正する。
４ 明細書２頁１行目
「片面亜鉛メッキ」とあるのを
「片面亜鉛系電気メッキ」に訂正する。
５ 明細書２頁８行目
「鉛メッキ」とあるのを
「鉛系電気メッキ」に訂正する。
６ 明細書３頁４行目
「片面亜鉛メッキ」とあるのを
「片面亜鉛系電気メッキ」に訂正する。
７、 明細書４頁１７行目〜１８行目
「片面電気亜鉛メッキ」とあるのを
「片面亜鉛系電気メッキ」と訂正する。
ａ 明細書５頁１行〜２行目
「水素イオン濃度（以下ＰＨとする）」 とあるのｔ−
ｒＰＨＪに訂正する。
９ 明細書５頁１６行目
「１０ ｏｈ／ｄｍ” Ｊ 金［２０ｏＡ／ａｆ Ｊに
訂正する。
１０ 明細書９頁１３行目と１４行目の間に「′実施
例１」を挿入する。
１１ 明細書９頁１４行目
１片面電気亜鉛メッキ」とあるのを
「片面亜鉛系電気メッキ」Ｋ訂正する。
１２ 明細書１０頁１０行目
［片面電気亜鉛メッキ］とあるのを
「片面亜鉛系電気メッキ」に訂正する。
１３ 明細書１２頁末行以下に次の文を挿入する。
実施例２
第２図に示す片面亜鉛系電気メツキ鋼板の製造設備にお
いて、メッキ浴組成として、ＺｎＳＯ４・７Ｈ２０２０
０ｆ／４Ｈ２ＳＯ４１０ｆ／Ｌ、 Ｎａ２ＳＯ４１００
ｔ／ｌ、 Ｎｉ ＳＯ４・６ Ｈ２Ｏ１６０ｆ／１％Ｆ
ｅＳＯ４−７Ｈ２０６０１／ｌ、 Ｃｒ２（ＳＯ４）３
２０？／ｌの硫酸性水溶液でＰＨ１，８、温度６０℃の
メッキ浴を用いた。
電解処理後の鉄面の評価およびリン酸塩処理条件、評価
基準は、実施例１と同様である。
次表の本発明例Ｔ、 Ｕ、 Ｖ、 Ｗは、鉄面の外観お
よびり／酸塩処理性が優れている。
別紙
上７未満の溶液中にて陽極電流密度２Ａ／ａｍ’以上で
電解処理を行い、非メッキ面の黒変を除去させると同時
にｎｏ５ｒ／ｍ’以下のリン酸鉄皮膜を非メツキ面上に
生成させることを特徴とする片面亜鉛系電気メツキ鋼板
の非メツ、キ面の後処理方法
特開ｏｇ５ｓ−３７１９２（８）FIG. 1 is an equipment layout diagram of a conventional single-sided electroplating apparatus, and FIGS. 2 and 3 are equipment layout diagrams of an example apparatus of the present invention. 1... Uncoiler 2... Shear 3... Welding machine 4... Degreasing tank 5... Washing tank
6... Pickling tank 7... Washing tank 8...
Electric plating tank 9... Washing tank 10... Dryer 11... Shear 12... Recoiler 13
...Electrolytic cell 14...Washing tank 15...Electrode 16...Press roll 17...Electrifying roll Applicant: Nippon Steel Corporation 11!3 Drawing procedure amendment (voluntary) 1982 January 12th Director General of the Japan Patent Office Mr. L Case Indication Patent Application No. 136608 2 of 1982
Title of the invention Post-treatment method 3 for the non-plated surface of single-sided electrogalvanized steel sheet Relationship with the case of the person making the amendment Patent applicant address 2-6-3 Otemachi, Chiyoda-ku, Tokyo Name (665) Made by Shin Nippon Tetsu Co., Ltd. Representative Takeshi 1)
Toyo 4 Agent Address: 103-241-044i Address: 1-14-2, Nihonbashi Honmachi, Chuo-ku, Tokyo Columns for the title of the invention, scope of claims, detailed description of the invention, and brief description of the drawings Amendment L The title of the invention is amended as follows. Post-treatment method 2 of non-plated surface of single-sided zinc-based electroplated steel sheet, the claims are amended as shown in the attached sheet. 3. On page 1, line 15 of the specification, [single-side electrogalvanizing] should be corrected to "single-side subnegative electroplating." 4. In the first line of page 2 of the specification, the phrase "single side galvanized" is corrected to "single side zinc-based electroplating." 5. On page 2, line 8 of the specification, "lead plating" should be corrected to "lead-based electroplating." 6. On page 3, line 4 of the specification, "single side zinc plating" is corrected to "single side zinc electroplating". 7. On page 4 of the specification, lines 17 to 18, the phrase "single-sided electrogalvanizing" is corrected to "single-sided zinc-based electroplating." a. Page 5 of the specification, lines 1 and 2, “Hydrogen ion concentration (hereinafter referred to as PH)” t-
Corrected to rPHJ. 9 Specification page 5 line 16 “10 oh/dm” J Gold [corrected to 20oA/af J. 10 Insert "'Example 1" between lines 13 and 14 on page 9 of the specification. 11 In the specification, page 9, line 14, 1st single-sided electrolytic galvanizing is corrected to read ``single-sided zinc-based electroplating''. 12. On page 10, line 10 of the specification, the phrase [single-sided electrolytic galvanizing] should be corrected to "single-sided zinc-based electroplating." 13 Insert the following sentence below the last line of page 12 of the specification. Example 2 In the production equipment for single-sided zinc-based electroplated steel sheets shown in FIG. 2, the plating bath composition was ZnSO4.7H2020.
0f/4H2SO410f/L, Na2SO4100
t/l, Ni SO4・6 H2O160f/1%F
eSO4-7H20601/l, Cr2(SO4)3
20? A plating bath with a pH of 1.8 and a temperature of 60° C. was used with a sulfuric acid aqueous solution of 1.2 liters. The evaluation of the iron surface after the electrolytic treatment, the phosphate treatment conditions, and the evaluation criteria were the same as in Example 1. Inventive examples T, U, V, and W in the following table are excellent in iron surface appearance and abrasive/acid treatment properties. Electrolytic treatment is performed at an anode current density of 2 A/am' or more in a solution with a concentration of less than 7 as shown in the attached sheet to remove black discoloration on the non-plated surface, and at the same time apply an iron phosphate film of no. 5 r/m' or less on the non-plated surface. Method for post-treatment of non-metal and exposed surfaces of single-sided zinc-based electroplated steel sheet, characterized by producing
Claims (1)
ッキを行なった後、非メッキ面を全リン酸濃度が０．０
５モル／を以上、水素イオン濃度４以上９未満の溶液中
にて陽極電流密度２ ｈ ／ ｄｒｒ１以上で電解処理
を行ない、非メッキ面の黒変を除去させると同時にｏ、
ｏ５ｒ／ｎ？以下のリン酸鉄を非メツキ面上に生成させ
ることを特徴とする片面電気亜鉛メッキ鋼板の非メッキ
面の後処理方法After electrogalvanizing a steel plate on one side in an aqueous solution for sulfuric acid acidic galvanic plating, the non-plated side was coated with a total phosphoric acid concentration of 0.0.
Electrolytic treatment is performed at an anode current density of 2 h/drr or more in a solution with a hydrogen ion concentration of 4 or more and less than 9 to remove black discoloration on the non-plated surface and at the same time o.
o5r/n? A method for post-treatment of a non-plated surface of a single-sided electrogalvanized steel sheet, characterized by producing the following iron phosphate on the non-plated surface:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13660881A JPS6028918B2 (en) | 1981-08-31 | 1981-08-31 | Post-treatment method for non-plated side of single-sided zinc-based electroplated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13660881A JPS6028918B2 (en) | 1981-08-31 | 1981-08-31 | Post-treatment method for non-plated side of single-sided zinc-based electroplated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5837192A true JPS5837192A (en) | 1983-03-04 |
| JPS6028918B2 JPS6028918B2 (en) | 1985-07-08 |
Family
ID=15179270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13660881A Expired JPS6028918B2 (en) | 1981-08-31 | 1981-08-31 | Post-treatment method for non-plated side of single-sided zinc-based electroplated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6028918B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0092342A2 (en) * | 1982-04-17 | 1983-10-26 | Nippon Steel Corporation | Method for producing a steel strip having an excellent phosphate-coating property |
| JPS60200974A (en) * | 1984-03-27 | 1985-10-11 | Nippon Kokan Kk <Nkk> | Post treatment of one-side electrogalvanized steel sheet |
| JPS63259084A (en) * | 1987-04-16 | 1988-10-26 | Kawasaki Steel Corp | Production of one-side zinc or zinc alloy electro-plated steel sheet |
| US4808278A (en) * | 1988-01-15 | 1989-02-28 | Armco Inc. | Method and apparatus for producing one-side electroplated steel strip with enhanced phosphatability |
| US4814054A (en) * | 1988-01-15 | 1989-03-21 | Armco Inc. | Apparatus for producing one-side electroplated steel strip with enhanced phosphatability |
-
1981
- 1981-08-31 JP JP13660881A patent/JPS6028918B2/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0092342A2 (en) * | 1982-04-17 | 1983-10-26 | Nippon Steel Corporation | Method for producing a steel strip having an excellent phosphate-coating property |
| JPS60200974A (en) * | 1984-03-27 | 1985-10-11 | Nippon Kokan Kk <Nkk> | Post treatment of one-side electrogalvanized steel sheet |
| JPS6334229B2 (en) * | 1984-03-27 | 1988-07-08 | Nippon Kokan Kk | |
| JPS63259084A (en) * | 1987-04-16 | 1988-10-26 | Kawasaki Steel Corp | Production of one-side zinc or zinc alloy electro-plated steel sheet |
| US4808278A (en) * | 1988-01-15 | 1989-02-28 | Armco Inc. | Method and apparatus for producing one-side electroplated steel strip with enhanced phosphatability |
| US4814054A (en) * | 1988-01-15 | 1989-03-21 | Armco Inc. | Apparatus for producing one-side electroplated steel strip with enhanced phosphatability |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6028918B2 (en) | 1985-07-08 |
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