JPH07278843A - Cold rolled steel sheet having excellent degreasability - Google Patents
Cold rolled steel sheet having excellent degreasabilityInfo
- Publication number
- JPH07278843A JPH07278843A JP7505294A JP7505294A JPH07278843A JP H07278843 A JPH07278843 A JP H07278843A JP 7505294 A JP7505294 A JP 7505294A JP 7505294 A JP7505294 A JP 7505294A JP H07278843 A JPH07278843 A JP H07278843A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- steel sheet
- degreasing
- rolled steel
- layer
- 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
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- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は自動車、家電用の冷延鋼
板にかかわり、化成処理前の脱脂性に優れた冷延鋼板を
提供する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold-rolled steel sheet for automobiles and home appliances, and provides a cold-rolled steel sheet having excellent degreasing property before chemical conversion treatment.
【０００２】[0002]
【従来の技術】自動車用鋼板や家電用鋼板は、実際の使
用に際してはプレス成形、溶接などを行った後、塗装下
地処理としての化成処理を行う。その後、その化成処理
皮膜の上に例えばカチオン電着塗装を行ったり、スプレ
ー塗装を行ったりして最終用途に使用される。この良好
な塗装性や塗装後耐食性を得るためには、良好な化成処
理性が必要不可欠である。この良好な化成処理性を得る
ためには、冷延鋼板の化成処理前の脱脂性が安定して良
好であり、後工程での化成皮膜結晶の核発生や成長を阻
害しないことが必要となる。2. Description of the Related Art Steel sheets for automobiles and steel sheets for home appliances are subjected to press forming, welding and the like before being actually used, and then subjected to chemical conversion treatment as a coating base treatment. Then, the chemical conversion coating is subjected to, for example, cationic electrodeposition coating or spray coating to be used for the final application. In order to obtain this good paintability and post-painting corrosion resistance, good chemical conversion treatability is essential. In order to obtain this good chemical conversion treatability, it is necessary that the degreasing property of the cold-rolled steel sheet before the chemical conversion treatment is stable and good, and that nucleation and growth of the chemical conversion film crystal in the subsequent step are not hindered. .
【０００３】自動車用、家電用鋼板として使用される冷
延鋼板は、従来はボックス焼鈍や連続焼鈍時の冷却を無
酸化雰囲気でのガスジェットクール等の方法で行ってい
た。そのため、化成処理皮膜の形成に有利とされるＭｎ
等の表面濃化層が存在するとともに水酸化鉄等の腐食生
成物の付着がないため、化成処理性に優れた鋼板であっ
た。しかし、最近材質作り込み強化のため上記連続焼鈍
時の冷却に水冷または気水冷却の方法を採用する傾向に
ある。この場合、冷却過程が酸化性雰囲気となるため、
鋼板表面に過剰の酸化膜を生成しブルーイングを生じ
る。したがって、この酸化膜を除去するため酸洗処理を
行う必要が生じる。しかし、この酸洗処理を行った鋼板
は、上述したＭｎ等の化成処理に有利な表面濃化層まで
除去したり、水酸化鉄を生成したりして化成処理性が劣
化した表面状態にある。Cold-rolled steel sheets used as steel sheets for automobiles and home appliances have conventionally been cooled by box annealing or continuous annealing by a method such as gas jet cooling in an non-oxidizing atmosphere. Therefore, Mn, which is advantageous for forming a chemical conversion coating,
A steel sheet having excellent chemical conversion treatability was obtained because there was a surface-enriched layer such as and the like and there was no adhesion of corrosion products such as iron hydroxide. However, recently, there has been a tendency to adopt a water cooling method or a water-water cooling method for cooling during the continuous annealing in order to strengthen the material incorporation. In this case, since the cooling process becomes an oxidizing atmosphere,
Excessive oxide film is formed on the surface of the steel sheet, causing bluing. Therefore, it is necessary to perform a pickling treatment to remove this oxide film. However, the steel sheet that has been subjected to this pickling treatment has a surface state in which the chemical conversion treatment property is deteriorated by removing even the surface concentrated layer of Mn or the like, which is advantageous for chemical conversion treatment, or forming iron hydroxide. .
【０００４】これに加えて、自動車、家電メーカーにて
化成処理を行う場合、量産ライン脱脂液、表面調整液、
化成処理液は経時変化を生じる。そこで、これら変動要
因に対しても良好な脱脂性を示し、結果として良好な化
成処理性を有する冷延鋼板が望まれていた。化成処理性
に劣る冷延鋼板表面の改善を図ったものとしては、特開
昭５６−１１６８８３号公報に冷延鋼板表面に金属Ｎｉ
を０．３〜１０ｍｇ／ｍ2 付着させる方法が開示されて
いる。金属Ｎｉを付着した冷延鋼板は、表面析出した金
属Ｎｉの局部電池の構成作用が極めて強く、化成処理反
応に対して極めて敏感な表面状態となっており、処理条
件の影響を非常に強く受ける。そのため、経時による変
動が大きい量産ライン液では安定して化成処理皮膜を生
成することができない。In addition to this, when carrying out chemical conversion treatment in automobiles and home electric appliances manufacturers, a degreasing liquid for the mass production line, a surface conditioning liquid,
The chemical conversion treatment liquid changes with time. Therefore, there has been a demand for a cold-rolled steel sheet that exhibits good degreasing properties with respect to these fluctuation factors and, as a result, has good chemical conversion treatability. As an attempt to improve the surface of the cold-rolled steel sheet which is inferior in chemical conversion treatment property, Japanese Patent Laid-Open No. 56-116883 discloses that metal Ni on the surface of the cold-rolled steel sheet.
Of 0.3 to 10 mg / m 2 is disclosed. The cold-rolled steel sheet having metallic Ni adhered thereto has a very strong local Ni constituent effect of the metallic Ni deposited on the surface, and has a very sensitive surface state to the chemical conversion treatment reaction, and is extremely affected by the treatment conditions. . Therefore, it is impossible to stably form the chemical conversion coating with the mass production line liquid, which greatly varies with time.
【０００５】また、特開昭５９−１５９９８７号公報に
は冷延鋼板表面にＮｉ酸化物または水酸化物をＮｉ元素
重量換算で１〜１５０ｍｇ／ｍ2 付着させたものが開示
されている。このＮｉの酸化物または水酸化物は、確か
に健全な脱脂液を使用した場合の化成処理性を向上させ
る。しかし、油との親和力が強いため、あらかじめ塗油
された防錆油や洗浄油がとれ難く、経時により油混入量
が多くなって脱脂性が劣化した脱脂液では十分に脱脂さ
れず、その結果として化成処理性が低下する。Further, JP-A-59-159987 discloses a cold-rolled steel sheet having Ni oxide or hydroxide deposited in an amount of 1 to 150 mg / m 2 in terms of Ni element weight. This Ni oxide or hydroxide certainly improves the chemical conversion treatability when a sound degreasing liquid is used. However, since it has a strong affinity with oil, it is difficult to remove rust-preventive oil or cleaning oil that has been preliminarily applied, and the degreasing liquid whose degreasing property has deteriorated due to an increase in the amount of oil mixed over time is not sufficiently degreased. As a result, the chemical conversion processability decreases.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上述のように
連続焼鈍時に水冷または気水冷却を受け、さらに酸洗処
理を行った冷延鋼板において、脱脂不良による化成処理
性の劣化がない、化成処理量産ラインの脱脂液変動の影
響を受けにくい脱脂性に優れた冷延鋼板を提供するもの
である。DISCLOSURE OF THE INVENTION The present invention, in the cold-rolled steel sheet subjected to water cooling or steam cooling during continuous annealing as described above and further subjected to pickling treatment, has no deterioration in chemical conversion treatability due to poor degreasing, It is intended to provide a cold-rolled steel sheet excellent in degreasing property that is hardly affected by fluctuations in degreasing liquid in a chemical conversion treatment mass production line.
【０００７】[0007]
【課題を解決するための手段】発明者らは、良好な脱脂
性が得られるとともに量産ラインの処理液の成分等の経
時による劣化に対して、金属Ｎｉのように化成処理条件
に敏感ではなく、同時に酸化Ｎｉまたは水酸化Ｎｉのよ
うに脱脂不良を生じない処理の検討を行うべく、種々の
研究を行った。その結果、鋼板表面の地鉄側に金属Ｎｉ
層を、最表層側に水酸化Ｎｉ層を有し、最表層のＮｉ存
在割合が７５〜９５ａｔｍ％の冷延鋼板が経時して劣化
した脱脂液中でも安定した脱脂性を示し、化成処理性が
良好であることを見い出すに至った。本発明は上記知見
に基いてなされたものであり、その要旨とするところ
は、鋼板表面に地鉄側に金属Ｎｉ層を、最表層に水酸化
Ｎｉ層を有し、最表層部のＮｉ存在割合が７５〜９５ａ
ｔｍ％、さらにＮｉが元素重量換算で１〜１００ｍｇ／
ｍ2 付着していることを特徴とする脱脂性に優れた冷延
鋼板にある。Means for Solving the Problems The inventors have obtained good degreasing properties and are not sensitive to chemical conversion treatment conditions such as metal Ni against deterioration with time of components of a treatment liquid in a mass production line. At the same time, various studies were conducted in order to investigate a treatment such as Ni oxide or Ni hydroxide which does not cause a degreasing failure. As a result, the Ni
The layer has a Ni hydroxide layer on the outermost layer side, and shows stable degreasing property even in a degreasing solution deteriorated over time of a cold-rolled steel sheet having a Ni presence ratio of 75 to 95 atm% in the outermost layer, and has chemical conversion treatability. We came to discover that it was good. The present invention has been made on the basis of the above findings, and the gist thereof is to have a metallic Ni layer on the base steel side on the steel plate surface, a nickel hydroxide layer on the outermost layer, and the presence of Ni on the outermost layer portion. Ratio is 75-95a
tm%, and Ni is 1 to 100 mg / in terms of element weight.
It is a cold rolled steel sheet excellent in degreasing property characterized by having m 2 attached.
【０００８】[0008]
【作用】以下本発明について説明する。金属Ｎｉ層は地
鉄との界面側になければならない。この金属Ｎｉの存在
により、冷延鋼板は脱脂後の化成処理において良好な反
応性を示す。水酸化Ｎｉは表層に存在し、下層の金属Ｎ
ｉが最表層に顔を出して化成処理液に対して過敏になり
すぎ、化成処理が不安定になるのを防ぐ。表層部のＮｉ
原子の存在割合は７５〜９５ａｔｍ％でなければならな
い。７５ａｔｍ％未満では水酸化Ｎｉ量が多く、油との
親和力が強いため脱脂性が低下してしまう。また、９５
ａｔｍ％より大きいと表層に金属Ｎｉが多量に存在し、
化成処理性を不安定にする。The present invention will be described below. The metallic Ni layer must be on the interface side with the ground iron. Due to the presence of this metallic Ni, the cold rolled steel sheet exhibits good reactivity in the chemical conversion treatment after degreasing. Ni hydroxide is present in the surface layer, and metal N in the lower layer
It prevents i from appearing in the outermost layer and becoming too hypersensitive to the chemical conversion treatment solution, which makes the chemical conversion treatment unstable. Ni in the surface layer
The abundance of atoms must be 75 to 95 atm%. If it is less than 75 atm%, the amount of Ni hydroxide is large and the affinity with oil is strong, so that the degreasing property is deteriorated. Also, 95
If it is larger than atm%, a large amount of metallic Ni exists in the surface layer,
It makes the chemical conversion processability unstable.
【０００９】Ｎｉ付着量をＮｉ元素重量換算で１〜１０
０ｍｇ／ｍ2 としたのは、１ｍｇ／ｍ2 未満では酸洗後
の冷延鋼板には化学溶解する箇所が少なく、その結果化
成結晶の核生成や成長が進まず化成処理反応特性が低下
し、スケとなるためである。また、１００ｍｇ／ｍ2 以
上では化成処理結晶が粗大化し外観が黒変するのとコス
ト高となるため好ましくない。The amount of Ni deposited is 1 to 10 in terms of Ni element weight.
0 mg / m 2 means that if it is less than 1 mg / m 2 , the cold-rolled steel sheet after pickling has few places to be chemically dissolved, and as a result, the nucleation and growth of the chemical conversion crystals do not proceed and the chemical conversion reaction characteristics deteriorate. This is because it becomes a scale. On the other hand, when the amount is 100 mg / m 2 or more, the chemical conversion treated crystal becomes coarse and the appearance becomes black and the cost becomes high, which is not preferable.
【００１０】[0010]
【実施例】厚さ０．８ｍｍのアルミキルド鋼を３％塩酸
にて酸洗した後、硫酸ニッケル５ｇ／ｌのＮｉめっき浴
から５Ａ／ｄｍ2 の電流密度でめっきを行った。また、
こうして作成した試料を表１に示す条件で化成処理を行
い、脱脂性および化成処理性を評価した。脱脂性につい
ては水漏れ面積にて評価し、化成処理性については化成
皮膜付着量、結晶粒径、外観にて評価を行った。EXAMPLE A 0.8 mm thick aluminum killed steel was pickled with 3% hydrochloric acid and then plated from a nickel plating bath of nickel sulfate 5 g / l at a current density of 5 A / dm 2 . Also,
The samples thus prepared were subjected to chemical conversion treatment under the conditions shown in Table 1 to evaluate degreasing property and chemical conversion treatability. The degreasing property was evaluated by the water leakage area, and the chemical conversion treatment property was evaluated by the amount of the chemical conversion film adhered, the crystal grain size, and the appearance.
【００１１】[0011]
【表１】 [Table 1]
【００１２】図１に表層部のＮｉ原子の存在割合と脱脂
性の関係を示す。これより、Ｎｉの存在割合が７５〜９
５ａｔｍ％で脱脂後の水漏れ性が良好で、その後の化成
処理性も良好であることがわかる。図２にＮｉ量と化成
処理後の結晶粒径および外観との関係を示す。結晶粒径
はＮｉ量が３０ｍｇ／ｍ2 を越えたくらいから増加しは
じめ、１００ｍｇ／ｍ2 を越えたところでは２０μｍを
越えている。また、外観も粒径が２０μｍを越えるＮｉ
量１００ｍｇ／ｍ2 以上で黒変がはじまる。FIG. 1 shows the relationship between the proportion of Ni atoms present in the surface layer and the degreasing property. From this, the existence ratio of Ni is 75 to 9
It can be seen that at 5 atm%, the water leakage property after degreasing is good, and the chemical conversion treatment property thereafter is also good. FIG. 2 shows the relationship between the amount of Ni and the crystal grain size and appearance after chemical conversion treatment. The crystal grain size starts to increase when the Ni content exceeds 30 mg / m 2, and exceeds 20 μm when the Ni content exceeds 100 mg / m 2 . In addition, the external appearance is Ni with a particle size exceeding 20 μm.
Blackening begins at an amount of 100 mg / m 2 or more.
【００１３】[0013]
【発明の効果】以上説明したように、本発明は連続焼鈍
時に水冷または気水冷却を受け、さらに酸洗処理を行っ
た冷延鋼板において、脱脂不良による化成処理性の劣化
がない、化成処理量産ラインの脱脂液変動の影響を受け
にくい脱脂性に優れた冷延鋼板を提供し、自動車、家電
製品の生産性向上に大きく貢献するものである。As described above, according to the present invention, the cold-rolled steel sheet subjected to water cooling or steam cooling during continuous annealing and further subjected to pickling treatment does not suffer deterioration of chemical conversion treatability due to poor degreasing. By providing cold-rolled steel sheets with excellent degreasing properties that are not easily affected by fluctuations in the degreasing liquid in the mass production line, it will greatly contribute to improving the productivity of automobiles and home appliances.
【図１】表層部のＮｉ原子の存在割合と脱脂性の関係を
示す図、FIG. 1 is a diagram showing the relationship between the abundance ratio of Ni atoms in the surface layer and degreasing property,
【図２】Ｎｉ量と化成処理後の結晶粒径および外観との
関係を示す図である。FIG. 2 is a diagram showing the relationship between the amount of Ni and the crystal grain size and appearance after chemical conversion treatment.
Claims (1)
層に水酸化Ｎｉ層を有し、最表層のＮｉ存在割合が７５
〜９５ａｔｍ％、さらにＮｉが元素重量換算で、１〜１
００ｍｇ／ｍ2 付着していることを特徴とする脱脂性に
優れた冷延鋼板。1. A metal Ni layer is provided on the base metal side of a steel sheet surface, and a nickel hydroxide layer is provided on the outermost layer, and the Ni presence ratio of the outermost layer is 75.
~ 95 atm%, and Ni is 1 to 1 in terms of element weight.
A cold-rolled steel sheet excellent in degreasing property, characterized in that it is adhered at 00 mg / m 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7505294A JP2957413B2 (en) | 1994-04-13 | 1994-04-13 | Cold rolled steel sheet with excellent degreasing properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7505294A JP2957413B2 (en) | 1994-04-13 | 1994-04-13 | Cold rolled steel sheet with excellent degreasing properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07278843A true JPH07278843A (en) | 1995-10-24 |
| JP2957413B2 JP2957413B2 (en) | 1999-10-04 |
Family
ID=13565051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7505294A Expired - Fee Related JP2957413B2 (en) | 1994-04-13 | 1994-04-13 | Cold rolled steel sheet with excellent degreasing properties |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2957413B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016268A (en) * | 2005-07-06 | 2007-01-25 | Jfe Steel Kk | Method for manufacturing steel sheet to be excellently degreased, and the steel sheet |
| JP2008190029A (en) * | 2007-01-12 | 2008-08-21 | Nippon Steel Corp | Cold rolled steel sheet having excellent degreasability and chemical convertibility |
| JP2021004391A (en) * | 2019-06-26 | 2021-01-14 | 住友電気工業株式会社 | Coating member, and method for producing coating member |
-
1994
- 1994-04-13 JP JP7505294A patent/JP2957413B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016268A (en) * | 2005-07-06 | 2007-01-25 | Jfe Steel Kk | Method for manufacturing steel sheet to be excellently degreased, and the steel sheet |
| JP2008190029A (en) * | 2007-01-12 | 2008-08-21 | Nippon Steel Corp | Cold rolled steel sheet having excellent degreasability and chemical convertibility |
| JP2021004391A (en) * | 2019-06-26 | 2021-01-14 | 住友電気工業株式会社 | Coating member, and method for producing coating member |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2957413B2 (en) | 1999-10-04 |
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