JPH0565698A - Production of electrolytically chromated steel sheet excellent in corrosion resistance and weldability - Google Patents
Production of electrolytically chromated steel sheet excellent in corrosion resistance and weldabilityInfo
- Publication number
- JPH0565698A JPH0565698A JP25445391A JP25445391A JPH0565698A JP H0565698 A JPH0565698 A JP H0565698A JP 25445391 A JP25445391 A JP 25445391A JP 25445391 A JP25445391 A JP 25445391A JP H0565698 A JPH0565698 A JP H0565698A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- chromium
- steel sheet
- tin
- plating
- 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)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、鋼板の表面上の第１
層としての金属クロム層上に金属錫およびクロム酸化物
からなる第２層が形成された耐食性および溶接性に優れ
た電解クロメート処理鋼板、あるいは、更に、前記第２
層の表面上に、金属クロムと水和クロム酸化物とからな
るクロメート被膜が形成された耐食性および溶接性に優
れた電解クロメート処理鋼板の製造方法に関するもので
ある。BACKGROUND OF THE INVENTION This invention relates to a first steel plate on the surface of a steel plate.
An electrolytic chromate-treated steel sheet excellent in corrosion resistance and weldability, in which a second layer made of metallic tin and chromium oxide is formed on a metallic chromium layer as a layer, or the second layer
The present invention relates to a method for producing an electrolytic chromate-treated steel sheet, which has a chromate coating composed of metallic chromium and hydrated chromium oxide formed on the surface of a layer and is excellent in corrosion resistance and weldability.
【０００２】[0002]
【従来の技術】鋼板の表面上に、下層としての金属クロ
ム層と、上層としてのクロム酸化物を主体とするクロム
水和酸化物層とからなる被膜が形成された電解クロメー
ト処理鋼板は、ブリキに比べて安価であることから、飲
料等の食缶、ペール缶、18リットル缶、オイル缶等の缶
用材料として、広い分野において、使用されている。従
来、この種の鋼板を用いる缶材は、主に、絞り加工によ
る２ピース缶、および、有機樹脂あるいは特殊セメント
を用いる接着缶（３ピース缶）として実用化されている
が、溶接缶としての利用割合は非常に小さい。その理由
は、電解クロメート処理鋼板が極めて溶接性に劣るため
である。その原因は、次の通りである。即ち、めっき層
を形成する、下層としての金属クロム層および上層とし
てのクロム水和酸化物層の非導電性および非伝熱性のた
めに、溶接電流によって発生する熱の発熱形態が不均一
となり、鋼が局部的に発熱し、チリ、ブローホール等の
溶接欠陥が生じ易いからである。2. Description of the Related Art An electrolytic chromate-treated steel sheet having a coating formed of a metal chromium layer as a lower layer and a chromium hydrated oxide layer mainly containing chromium oxide as an upper layer on the surface of a steel sheet is a tin plate. Since it is cheaper than, it is used in a wide range of fields as a material for cans such as beverage cans, pail cans, 18 liter cans, and oil cans. Conventionally, a can material using this type of steel sheet has been practically used mainly as a two-piece can made by drawing and an adhesive can (3 piece can) using an organic resin or special cement. The usage rate is very small. The reason is that the electrolytic chromate treated steel sheet has extremely poor weldability. The cause is as follows. That is, because of the non-conductivity and non-heat transfer properties of the metal chrome layer as the lower layer and the chromium hydrated oxide layer as the upper layer which form the plating layer, the heat generation form of the heat generated by the welding current becomes non-uniform, This is because the steel locally generates heat and welding defects such as dust and blowholes are likely to occur.
【０００３】このため、従来は、敢えて通常の電解クロ
メート処理鋼板を溶接するような場合には、溶接部とな
るクロメート処理被膜を研磨除去してから溶接するとい
う煩雑な方法を採っていた。しかしながら、近年、強度
および信頼性の高い溶接缶の需要が高まっていることか
ら、電解クロメート処理鋼板の溶接性の向上が要求さ
れ、被膜を研磨除去しないで溶接できる電解クロメート
処理鋼板の開発が望まれている。For this reason, conventionally, in the case of intentionally welding an ordinary electrolytic chromate-treated steel sheet, a complicated method of polishing and removing the chromate-treated film to be the welded portion and then welding was adopted. However, in recent years, the demand for welded cans with high strength and reliability is increasing, so improvement in the weldability of electrolytic chromate-treated steel sheets is required, and the development of electrolytic chromate-treated steel sheets that can be welded without polishing removal of the coating film is desired. It is rare.
【０００４】電解クロメート処理鋼板の溶接性の向上を
狙った従来技術の１つとして、特公昭63−35718 号公報
および特開昭60−262975号公報に代表されるような、金
属クロム層上に錫を被覆させ、溶接性の向上を図ったも
のがある。しかし、これら先行技術は、金属クロム層上
に錫を被覆させるために、特殊な前処理または錫めっき
を施すため、錫の下層である金属クロムの均一性が欠
け、耐食性が劣る傾向にあり、さらに、錫層上にクロメ
ート処理を行うことが必須条件であった。この耐食性の
低下は、錫めっき量を多めに付着させることによっても
補うことは可能ではあるが、安価な材料を開発目標にし
ている思想に反するばかりでなく、耐糸状錆び性に対し
ては、効果がなく、逆に糸状錆びが発生し易くなるとい
う問題を抱えていた。As one of the conventional techniques aimed at improving the weldability of electrolytic chromate-treated steel sheets, a metal chromium layer is typified by JP-B-63-35718 and JP-A-60-262975. There is a coating of tin to improve weldability. However, in these prior arts, in order to coat tin on the metal chromium layer, a special pretreatment or tin plating is performed, so that the metal chromium that is the lower layer of tin lacks uniformity and tends to have poor corrosion resistance. Furthermore, it was an essential condition to perform chromate treatment on the tin layer. This decrease in corrosion resistance can be compensated by adding a large amount of tin plating, but not only against the idea of developing a cheap material as a development goal, but also for the thread-like rust resistance, There was a problem that it was not effective and, conversely, filiform rust was likely to occur.
【０００５】そこで、本発明者等は、これら問題点を解
決すべく研究を重ね、既に、特願平１−104258号「耐食
性および溶接性に優れた電解クロメート処理鋼板および
その製造方法」に示したような、新規な素材ならびにそ
の製造方法の発明に到った。Therefore, the inventors of the present invention have conducted extensive research to solve these problems, and have already shown in Japanese Patent Application No. 1-104258, "Electrolytic chromate treated steel sheet excellent in corrosion resistance and weldability and its manufacturing method". As described above, the invention of a novel material and a manufacturing method thereof has been reached.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上述の
特願平１−104258号のような、第１層としての金属クロ
ム層の表面上に錫ならびにクロム酸化物からなる第２層
としてのめっき層を形成した新規な素材の製造におい
て、金属クロム層上の、錫ならびにクロム酸化物からな
るめっき層の良好な密着性、あるいは、むらの無い良好
な外観が、安定性良く得られないという問題がある。ま
た、このような錫ならびにクロム酸化物からなるめっき
を行うためのめっき浴中では、めっき電解中に錫スラッ
ジ（錫の酸化沈澱物）の生成が早く、その結果として浴
劣化が早まり、めっきの安定操業を損なうという問題も
残されている。However, as in the above-mentioned Japanese Patent Application No. 1-104258, the plating layer as the second layer made of tin and chromium oxide is formed on the surface of the metal chromium layer as the first layer. In the production of a new material having the above-mentioned structure, there is a problem that good adhesion of a plating layer made of tin and chromium oxide on a metal chromium layer, or good appearance without unevenness cannot be obtained with good stability. is there. In addition, in a plating bath for plating such tin and chromium oxide, tin sludge (tin oxide precipitate) is rapidly generated during plating electrolysis, resulting in accelerated bath deterioration and There is also the problem of impairing stable operation.
【０００７】電気クロムめっきによって形成された金属
クロムめっき層の表面には、常にクロム水和酸化物が存
在することから、電気クロムめっき後、更に異種の金属
めっきを施す場合、このクロム水和酸化物の存在のため
に、密着性が良く、外観も良好な異種金属めっき層が得
られないことが知られている。そこで、例えば、金属ク
ロムめっき層の表面上に錫めっきを行う場合は、特公昭
63−35718 号公報および特開昭61−130500号公報に開示
されているように、錫めっき液中の錫含有量（錫濃度）
を通常濃度より低下させたり、あるいは、酸性度を上げ
ることにより、錫の電解効率を落として電気錫めっきを
行い、その結果、錫めっき時に多量の水素ガスがクロム
めっき表面上で発生し、その水素ガスによって金属クロ
ム表面上の水和クロム酸化物が除去されて表面が活性化
されると同時に錫めっきが行われ、密着性に優れた錫め
っき被膜を得るというような特殊な処理が必要である。Since the hydrated chromium oxide is always present on the surface of the metallic chrome plating layer formed by electrochromic plating, when different metal plating is further applied after electrochromic plating, this hydrated chromium oxide is used. It is known that a dissimilar metal plating layer having good adhesion and good appearance cannot be obtained due to the presence of a substance. Therefore, for example, when performing tin plating on the surface of the metal chromium plating layer,
As disclosed in 63-35718 and JP-A-61-130500, the tin content (tin concentration) in the tin plating solution.
To lower the normal concentration or increase the acidity to reduce the electrolytic efficiency of tin and perform electrotin plating, and as a result, a large amount of hydrogen gas is generated on the chromium plating surface during tin plating. Hydrogen gas removes hydrated chromium oxides on the surface of metallic chromium and activates the surface, and at the same time tin plating is performed, and special treatment such as obtaining a tin plating film with excellent adhesion is required. is there.
【０００８】この発明の電解クロメート処理鋼板の製造
においても、前記類似先行技術の金属クロム上への錫め
っき方法の場合と考え方を同じくして、金属クロム上の
第２層めっきを行う際に、多量の水素ガスをめっきと同
時に発生させればよい。しかし、確かに、このような公
知の技術思想により、第２層のめっき密着性は改善され
るが、むらの無い外観が良好な表面を安定して得られな
い。Also in the production of the electrolytic chromate-treated steel sheet of the present invention, when the second layer plating on metal chromium is carried out, the same idea as in the tin plating method on metal chromium of the prior art similar to the above is used. A large amount of hydrogen gas may be generated at the same time as plating. However, although such a known technical idea certainly improves the plating adhesion of the second layer, it is not possible to stably obtain a surface having a uniform appearance and a good appearance.
【０００９】従って、この発明の目的は、金属クロムめ
っき層の表面上に、錫およびクロム酸化物からなるめっ
き層を有する、耐食性および溶接性に優れた電解クロメ
ート処理鋼板の製造において、密着性の良好な、且つ、
むらの無い外観の良好な錫およびクロム酸化物からなる
めっき層が得られ、同時に錫およびクロム酸化物からな
るめっきを行うめっき浴中の錫スラッジ（錫の酸化沈澱
物）の生成を抑制できる方法を提供することにある。Therefore, an object of the present invention is to produce an adhesive layer in the production of an electrolytic chromate-treated steel sheet having a plating layer made of tin and chromium oxide on the surface of a metal chromium plating layer, which is excellent in corrosion resistance and weldability. Good and
A method capable of obtaining a plating layer composed of tin and chromium oxide having a good appearance without unevenness, and at the same time suppressing the formation of tin sludge (tin oxide precipitate) in a plating bath for plating of tin and chromium oxide To provide.
【００１０】[0010]
【課題を解決するための手段】本発明者等は、上述した
問題にからみ、鋼板の表面上に第１層としての金属クロ
ム層と第２層としての錫およびクロム酸化物からなるめ
っき層を有する電解クロメート処理鋼板を製造するにあ
たり、第２層のめっきの密着性不良あるいはむらの発生
原因、ならびに第２層めっき浴中の錫スラッジ生成原因
について鋭意研究を重ねた。その結果、次の知見を得
た。 密着性不良は、金属クロム上のクロム酸化物が十分
取り除かれていないことに起因しており、第２層めっき
時に同時に水素ガスを多量に発生させれば改善される。
しかし、むらは、この水素ガスの発生に起因しており、
即ち、処理鋼板表面からの水素ガスの離脱性が関係して
おり、処理鋼板界面の攪拌を促進し、発生する水素ガス
の離脱を加速させてやらなければ、むらは解消されな
い。 錫スラッジ（錫の酸化沈澱物）の生成には、通常の
錫めっきの際と同じく、錫ならびにクロム混合めっき浴
中の溶存酸素、あるいは、めっき電極（アノード）上で
発生する酸素による液相酸化、ならびに、めっき電極上
での直接酸化が少なからず関与し、更に、本処理方法に
おいては、錫イオンと同時に存在するクロムが、錫の酸
化に関与している。In view of the above-mentioned problems, the present inventors have formed a metal chromium layer as the first layer and a plating layer made of tin and chromium oxide as the second layer on the surface of the steel sheet. In manufacturing the electrolytic chromate-treated steel sheet, the inventors conducted extensive studies on the cause of poor adhesion or unevenness of the second layer plating and the cause of tin sludge formation in the second layer plating bath. As a result, the following findings were obtained. The poor adhesion results from the fact that the chromium oxide on the metallic chromium is not sufficiently removed, and can be improved by generating a large amount of hydrogen gas at the same time as the second layer plating.
However, the unevenness is caused by the generation of this hydrogen gas,
That is, the desorption of hydrogen gas from the surface of the treated steel sheet is involved, and the unevenness cannot be resolved unless the stirring of the interface of the treated steel sheet is promoted and the desorption of the generated hydrogen gas is accelerated. As with ordinary tin plating, tin sludge (tin oxide precipitate) is generated by liquid phase oxidation by dissolved oxygen in the tin and chromium mixed plating bath or by oxygen generated on the plating electrode (anode). In addition, direct oxidation on the plated electrode is not a little involved, and in the present treatment method, chromium present at the same time as tin ions is involved in the oxidation of tin.
【００１１】この発明は、上述の知見に基づいてなされ
たものであって、鋼板上の第１層としての金属クロム層
の表面上に、金属錫ならびにクロム酸化物からなる第２
層が形成された耐食性および溶接性に優れた電解クロメ
ート処理鋼板あるいは、更に、前記第２層の表面上に、
金属クロム層および水和クロム酸化物とからなるクロメ
ート被膜が形成された耐食性および溶接性に優れた電解
クロメート処理鋼板に関して、第２層めっき層の密着性
の改善、むらの防止、ならびに、第２層を形成するため
のめっき浴中のスラッジ抑制を同時に可能ならしめる新
規な製造方法の発明である。The present invention has been made on the basis of the above-mentioned findings, and a second layer of metallic tin and chromium oxide is formed on the surface of a metallic chromium layer as a first layer on a steel sheet.
An electrolytic chromate treated steel sheet having a layer formed thereon and excellent in corrosion resistance and weldability, or further, on the surface of the second layer,
Regarding an electrolytic chromate-treated steel sheet excellent in corrosion resistance and weldability in which a chromate coating composed of a metal chromium layer and a hydrated chromium oxide is formed, improvement in adhesion of the second layer plating layer, prevention of unevenness, and second It is an invention of a novel manufacturing method that simultaneously enables sludge suppression in a plating bath for forming a layer.
【００１２】第１の発明は、鋼板に電気クロムめっきを
施して前記鋼板の少なくとも一方の表面上に30から300m
g/ m2 の範囲内の付着量の金属クロムからなる第１層を
形成し、次いで、前記第１層が形成された鋼板を水洗
し、次いで、水洗後直ちに、前記第１層が形成された鋼
板に対して、5 から50g/l の範囲内の硫酸クロムおよび
3 から15g/l の範囲内の錫(Sn)イオンを含有し、硫酸換
算で45から120 g/l の範囲内の酸濃度の水溶液中におい
て、50A/dm2 超150A/dm 2 以下の範囲内の電流密度によ
って陰極電解処理を施すことにより、前記第１層の表面
上に、金属錫換算で(1000/X)＋50から(30000/X) ＋50mg
/m2 ( 但し、X は、前記第１層中の金属クロム付着量で
ある）の範囲内の付着量の錫およびクロム換算で２から
30mg/ m2 の範囲内の付着量のクロム酸化物からなる第
２層を形成することにより、前記水溶液からなるめっき
浴の劣化を抑制するとともに、前記第１層の表面上に、
密着性に優れ、むらのない良好な表面外観を有する前記
第２層を形成することに特徴を有するものである。第２
の発明は、前記第２層の表面上に、１から30mg/m2 の範
囲内の付着量の水和酸化物からなるクロメート被膜を形
成することに特徴を有するものである。第３の発明は、
前記第２層の表面上に、３から30mg/m2 の範囲内の付着
量の金属クロム層を形成し、次いで、前記金属クロム層
の表面上に、１から30mg/m2 の範囲内の付着量の水和酸
化物からなるクロメート被膜を形成することに特徴を有
するものである。第４の発明は、前記水溶液中に、ナフ
チル基にオキシエチレン鎖の付加したノニオン系界面活
性剤を1 〜8 g/l 含有させることに特徴を有するもので
ある。In a first invention, a steel plate is electrochromized to form 30 to 300 m on at least one surface of the steel plate.
forming a first layer consisting of an amount of metallic chromium deposited in the range of g / m 2 , then washing the steel sheet on which the first layer has been formed with water, and then immediately after washing with water, forming the first layer Chrome sulfate in the range of 5 to 50 g / l and
3 contains tin (Sn) ions within the range of 15 g / l, in an aqueous solution of an acid concentration in the range of from 45 to 120 g / l sulfuric acid in terms of, 50A / dm 2 Ultra 150A / dm 2 or less in the range By applying cathodic electrolysis treatment according to the current density inside, (1000 / X) +50 to (30000 / X) +50 mg in terms of metallic tin on the surface of the first layer.
/ m 2 (where X is the amount of metallic chromium deposited in the first layer) within a range of 2 to 2 in terms of tin and chromium in terms of tin and chromium.
By forming the second layer composed of the chromium oxide having an adhesion amount within the range of 30 mg / m 2 , deterioration of the plating bath composed of the aqueous solution is suppressed and at the same time, on the surface of the first layer,
It is characterized by forming the second layer having excellent adhesion and a good surface appearance without unevenness. Second
The invention of (1) is characterized in that a chromate film made of a hydrated oxide having an adhesion amount in the range of 1 to 30 mg / m 2 is formed on the surface of the second layer. The third invention is
A metal chromium layer having a deposition amount in the range of 3 to 30 mg / m 2 is formed on the surface of the second layer, and then a metal chromium layer in the range of 1 to 30 mg / m 2 is formed on the surface of the metal chromium layer. It is characterized by forming a chromate film composed of an attached amount of hydrated oxide. A fourth aspect of the invention is characterized in that the aqueous solution contains 1 to 8 g / l of a nonionic surfactant having an oxyethylene chain added to a naphthyl group.
【００１３】以下、この発明を具体的に説明する。この
発明では、まず、鋼板の表面に電気クロムめっきを行
う。電気クロムめっきを行う鋼板は特に限定されない
が、通常は、冷間圧延された冷延鋼板を用いればよい。
また、電気クロムめっき前の前処理方法は、用いられる
鋼板の表面状態によって任意に決定すればよく、必要に
応じて種々の処理を行って構わない。The present invention will be specifically described below. In the present invention, first, the surface of the steel sheet is electroplated with chromium. The steel plate on which electrochromic plating is performed is not particularly limited, but normally a cold rolled cold rolled steel plate may be used.
Further, the pretreatment method before electrochromic plating may be arbitrarily determined according to the surface condition of the steel sheet used, and various treatments may be performed as necessary.
【００１４】電気クロムめっき方法は、特定の処理方法
に制限するものではなく、従来より公知のクロムめっき
浴、めっき方法を用いればよい。即ち、無水クロム酸あ
るいはクロム酸塩の１種または２種以上を主体として、
それに助剤として、硫酸、硫酸塩、フッ化物のうち１種
または２種以上を含むクロムめっき液で、鋼板を陰極と
して、所定量のクロムが付着するように電解すればよ
い。The electrochrome plating method is not limited to a specific treatment method, and a conventionally known chromium plating bath or plating method may be used. That is, mainly one or more of chromic anhydride or chromate,
In addition, a chromium plating solution containing one or more of sulfuric acid, sulfate, and fluoride as an auxiliary agent may be electrolyzed so that a predetermined amount of chromium adheres to the steel plate as a cathode.
【００１５】電気クロムめっきの電解電流密度は、とく
に限定するものではないが、好ましくは70A/dm2 以上で
行ったほうが良い。これは、次の理由からである。即
ち、第２層としてのめっき層の密着性が良く、均一なめ
っき（むらの無い第２層めっき）を行うために、第２層
めっき処理に供されるクロムめっき鋼板表層の水和クロ
ム酸化物の量は、出来るだけ少なくした方が良い。その
ためには、クロムめっき終了時点において、不可避的に
存在する水和クロム酸化物の量を、最低レベルにまで抑
えることができれば、より有効である。公知のクロムめ
っき技術において、水和クロム酸化物の量を抑える方法
は種々知られているが、70A/dm2 以上の電流密度におい
て電気クロムめっきを行う方法によっても、不可避的に
存在する水和クロム酸化物の量を、最低レベルにまで落
とすことができる。また、70A/dm2 以上の高電流密度で
処理すれば、クロムめっき設備の短縮化も図られるとい
う付随的効果も期待できる。The electrolytic current density of the electrochromic plating is not particularly limited, but preferably 70 A / dm 2 or more. This is for the following reason. That is, the hydrated chromium oxide on the surface layer of the chromium-plated steel sheet subjected to the second layer plating treatment in order to perform uniform plating (second layer plating without unevenness) with good adhesion of the plated layer as the second layer. It's best to keep the amount of things as small as possible. For that purpose, it is more effective if the amount of hydrated chromium oxides unavoidably present at the time of completion of chromium plating can be suppressed to the minimum level. In the known chrome plating technology, various methods for suppressing the amount of hydrated chrome oxide are known, but the hydration that is unavoidable also exists by the method of performing electrochrome plating at a current density of 70 A / dm 2 or more. The amount of chromium oxide can be reduced to the lowest level. If the treatment is performed at a high current density of 70 A / dm 2 or more, the additional effect of shortening the chromium plating equipment can be expected.
【００１６】電気クロムめっきの金属クロムの形態につ
いては、なんら規定するものではなく、粒状金属クロ
ム、板状金属クロムを含むものである。従って、前記電
気クロムめっき処理直前、または、その途中に処理鋼板
を陽極とする逆電解処理を施して、意識的に粒状金属ク
ロムを形成させても何等差し支えない。The form of metallic chromium in the electrochromic plating is not specified at all, and includes granular metallic chromium and plate metallic chromium. Therefore, it does not matter if the granular metal chromium is intentionally formed by performing the reverse electrolysis treatment using the treated steel plate as an anode immediately before or during the electrochromic plating treatment.
【００１７】金属クロムの付着量は、30から300mg/m 2
の範囲内に限定すべきである。金属クロム付着量が30mg
/m2 未満では、後述する錫の合金化抑制効果が十分に現
れず、しかも、溶接性を付与するために存在させる金属
錫が多量に必要となり、塗装焼付け条件によっては、糸
状錆び性が低下するなど耐食性に問題が生ずる。一方、
金属クロム付着量が300mg/m 2 を超えても、錫の合金化
抑制効果は向上せず、コスト高となる。The adhesion amount of metallic chromium is 30 to 300 mg / m 2
Should be limited to within the range. Adhesion amount of metallic chromium is 30 mg
If it is less than / m 2 , the effect of suppressing the alloying of tin, which will be described later, does not sufficiently appear, and moreover, a large amount of metallic tin that is present to impart weldability is required, and depending on the paint baking conditions, the thread-like rust resistance decreases. There is a problem in corrosion resistance. on the other hand,
Even if the amount of deposited metallic chromium exceeds 300 mg / m 2 , the effect of suppressing alloying of tin is not improved and the cost is increased.
【００１８】このように、電気クロムめっきを行った
後、続いて、十分な水洗洗浄処理を行い、表面を乾かす
ことなく、引き続き、5 から50g/l の範囲内の硫酸クロ
ムおよび3 から15g/l の範囲内の錫(Sn)イオンを含有
し、硫酸換算で45から120g/lの範囲の水溶液中におい
て、50A/dm2 超150A/ dm2以下の範囲内の電流密度で前
記鋼板に陰極電解処理を施して所定量の錫および所定量
のクロム酸化物からなる第２層めっきを行う。クロムメ
ッキ後の水洗は、金属クロム表面のむらを無くすために
も十分に行ったほうがよい。また、水洗水の温度は50℃
以下が良く、好ましくは30℃以下である。これは、電気
めっき時の鋼板のジュール熱、あるいは水洗水温度のた
めに、電気クロムメッキ表面温度が上昇し、後の第２層
メッキの際に表層の水和クロム酸化物が除去しにくくな
る方向に、その構造を変化させないために有効である。In this way, after the electrochromic plating is performed, a sufficient washing treatment with water is carried out, and the surface is not dried, and then chromium sulfate in the range of 5 to 50 g / l and 3 to 15 g / l are continuously added. In an aqueous solution containing tin (Sn) ions in the range of l, converted to sulfuric acid in the range of 45 to 120 g / l, a cathode is applied to the steel sheet at a current density in the range of more than 50 A / dm 2 and not more than 150 A / dm 2. An electrolytic treatment is performed to perform second layer plating of a predetermined amount of tin and a predetermined amount of chromium oxide. Washing with water after chrome plating should be thoroughly performed to eliminate unevenness on the surface of metal chrome. The temperature of the wash water is 50 ° C.
The following is good, and preferably 30 ° C or lower. This is because the surface temperature of the electrochromic plating increases due to the Joule heat of the steel sheet during electroplating or the temperature of washing water, and it becomes difficult to remove the hydrated chromium oxide on the surface layer during the subsequent second layer plating. It is effective in not changing its structure in the direction.
【００１９】クロム上へのクロム酸化物を含む錫めっき
には、めっきの際に、水素ガスを発生させ、このガスに
より水和酸化物を除去しながら同時にめっきするという
方法が有効であるが、表面外観が不安定であったり、ス
ラッジ生成による第２層めっき液の劣化が問題であっ
た。本発明者等は、これら問題解決策について検討を続
けた結果、第２層めっき液の劣化を防止するとともに、
同時に安定して良好なめっき外観が得られる第２層めっ
き方法を新規に見出した。For tin plating containing chromium oxide on chromium, it is effective to generate hydrogen gas during plating and simultaneously remove the hydrated oxide by this gas and perform plating at the same time. There are problems that the surface appearance is unstable and that the second layer plating solution deteriorates due to sludge formation. The present inventors, as a result of continuing studies on these problem solving methods, prevent the deterioration of the second layer plating solution, and
At the same time, we have newly found a second layer plating method that can stably obtain a good plating appearance.
【００２０】この発明の第２層めっき液中の硫酸クロム
含有量（硫酸クロム濃度）は、５から50g/l の範囲内で
ある。硫酸クロム含有量が５g/l未満では、クロム酸化
物が生成されず、錫の析出も粉状になる。一方、硫酸ク
ロム含有量が50g/l を超えると、鋼板の表面色調がやや
青白くなるだけで性能的に問題ないが、経済的でない。The chromium sulfate content (chromium sulfate concentration) in the second layer plating solution of the present invention is in the range of 5 to 50 g / l. When the content of chromium sulfate is less than 5 g / l, no chromium oxide is formed and tin is also precipitated in powder form. On the other hand, when the content of chromium sulfate exceeds 50 g / l, the surface color tone of the steel sheet becomes slightly pale and there is no problem in performance, but it is not economical.
【００２１】この発明の第２層めっき液中の錫イオン含
有量（錫イオン濃度）は、３から15g/l 、好ましくは、
３から８g/l の範囲内とすべきである。錫イオン含有量
が３g/l 未満では、錫の電解効率が極端に低下し、非効
率的であると同時に、錫イオン濃度管理も難しくなり、
好ましくない。一方、錫イオン含有量が15g/l を超える
と、析出する錫が粉状になり、密着性および外観が極端
に悪くなる。用いられる錫イオンの供給は、特定の錫化
合物に限定されず、酸化第１錫、塩化錫、硫酸錫、ホウ
フッ化錫、あるいは、その他の錫化合物が使用できる。The tin ion content (tin ion concentration) in the second layer plating solution of the present invention is 3 to 15 g / l, preferably
It should be in the range of 3 to 8 g / l. If the tin ion content is less than 3 g / l, the electrolysis efficiency of tin is extremely lowered, which is inefficient, and at the same time, the tin ion concentration control becomes difficult,
Not preferable. On the other hand, when the tin ion content exceeds 15 g / l, the precipitated tin becomes powdery, and the adhesion and the appearance are extremely deteriorated. The supply of tin ions used is not limited to a specific tin compound, and stannous oxide, tin chloride, tin sulfate, tin borofluoride, or other tin compounds can be used.
【００２２】この発明の錫めっき液中の酸濃度は、硫酸
換算で45g/l以上、好ましくは60g/l 以上とすべきであ
る。酸濃度が硫酸換算で45g/l 未満では、第２層めっき
液中のスラッジ生成速度が早くなり、めっき液の劣化が
早まり、第２層めっきの連続処理性が悪化すると同時に
処理コストもアップする。一方、酸濃度が硫酸換算で45
g/l 以上では、スラッジの生成が抑制され、連続的に安
定した第２層めっき処理が可能である。スラッジは、め
っき液中の錫イオン (Sn2+) が酸化されて(Sn4+) 錫酸
化物として沈澱を起こした白色系の微粒子である。これ
が、めっき液中に多量に存在すると、時として、鋼板表
面への付着を生じ、めっき表面の押し疵、あるいは電気
給電部におけるアークスポット欠陥の原因となる。特
に、この発明の第２層めっき液中には、硫酸クロム添加
によるクロムイオンが混入するが、このクロムイオンが
何らかの作用をし、スラッジ生成を促進することが分か
った。従って、金属クロム層上へのクロム酸化物含有錫
めっき処理の場合、密着性良好な、外観性に優れためっ
きを行うと同時に、めっき処理時のスラッジ生成を抑え
ることが重要となる。この発明のように酸濃度を硫酸換
算で45g/l 以上にすると、スラッジ生成が抑制される
が、これは、錫酸化物の溶解度が増加して、錫イオンと
して錫めっき液中に存在しやすくなるためと考えられ
る。また、酸濃度の上限は120g/lとする。酸濃度が高く
なりすぎると、腐食性が増し、めっき装置の劣化を早め
ることが予想される。The acid concentration in the tin plating solution of the present invention should be 45 g / l or more, preferably 60 g / l or more in terms of sulfuric acid. If the acid concentration is less than 45 g / l in terms of sulfuric acid, the sludge generation rate in the second layer plating solution will increase, the plating solution will deteriorate faster, and the continuous processability of the second layer plating will deteriorate and the processing cost will increase at the same time. .. On the other hand, the acid concentration is 45 in terms of sulfuric acid.
Above g / l, the generation of sludge is suppressed and a continuous and stable second layer plating process is possible. Sludge is white fine particles in which tin ions (Sn 2+ ) in the plating solution are oxidized and precipitated as (Sn 4+ ) tin oxide. When a large amount of this is present in the plating solution, it sometimes adheres to the surface of the steel plate, causing a flaw on the plating surface or an arc spot defect in the electric power feeding portion. In particular, it was found that chromium ions due to the addition of chromium sulfate are mixed in the second layer plating solution of the present invention, and the chromium ions have some action to promote sludge formation. Therefore, in the case of the chromium oxide-containing tin plating treatment on the metal chromium layer, it is important to suppress the generation of sludge during the plating treatment while performing the plating with good adhesion and excellent appearance. When the acid concentration is 45 g / l or more in terms of sulfuric acid as in the present invention, sludge formation is suppressed, but this is because the solubility of tin oxide is increased, and it tends to be present in the tin plating solution as tin ions. It is thought to be because. The upper limit of the acid concentration is 120 g / l. If the acid concentration becomes too high, it is expected that the corrosiveness will increase and the deterioration of the plating equipment will be accelerated.
【００２３】第２層めっきの陰極電流密度は、50A/dm2
超150A/dm 2 以下とすべきである。電流密度が50A/dm2
以下では、単位時間当たりの水素ガス発生量が少なく、
発生した水素ガスによる鋼板表面の攪拌が不十分とな
り、水素ガスの鋼板表面からの離脱が遅れるのと同時
に、水和クロム酸化物の除去も不十分となり、部分的な
錫めっき密着不良および部分的錫めっき付着量の差が生
じることによるめっきむらが発生し、安定して外観良好
な第２層めっきが得られない。50A/dm2超の電流密度で
処理することにより、上記問題が解決され、良好な外観
が得られる。一方、電流密度が150A/dm 2 を超えると、
水素ガス発生量が多くなり過ぎて錫の電着が妨げられ
る。The cathode current density of the second layer plating is 50 A / dm 2
It should be a super-150A / dm 2 or less. Current density is 50 A / dm 2
Below, the amount of hydrogen gas generated per unit time is small,
Stirring of the steel sheet surface due to the generated hydrogen gas becomes insufficient, and the release of hydrogen gas from the steel sheet surface is delayed, and at the same time, the removal of hydrated chromium oxide becomes insufficient, resulting in partial poor tin plating adhesion and partial The unevenness of the plating occurs due to the difference in the amount of the tin plating deposited, and the second layer plating having a good appearance cannot be stably obtained. By treating with a current density of more than 50 A / dm 2 , the above problems are solved and a good appearance is obtained. On the other hand, if the current density exceeds 150 A / dm 2 ,
The amount of hydrogen gas generated is too large to prevent the electrodeposition of tin.
【００２４】第２層のめっき浴温度は、30から50℃の範
囲内で任意に設定するのが望ましい。The temperature of the plating bath for the second layer is preferably set within the range of 30 to 50 ° C.
【００２５】この発明の第２層めっき中の錫付着量は、
金属錫換算で、(1000/X)＋50mg/m2 から(30000/X) ＋50
mg/m2 の範囲内である。錫付着量が、金属錫換算で、(1
000/X)＋50mg/m2 未満では、塗装焼付け時の熱によっ
て、金属錫と鋼との合金が形成され、この結果、金属錫
が減少して、溶接性が不十分となる。一方、錫付着量
が、金属錫換算で、(30000/X) ＋50mg/m2 を超えると、
金属錫が必要以上に残り、経済的に不利である。このよ
うな理由から、第２層めっき中の錫付着量が限定されて
いる。また、第２層中のクロム酸化物付着量は、クロム
換算で、１から30mg/m2 の範囲内とすべきである。クロ
ム酸化物付着量がクロム換算で１mg/m2 未満では、耐食
性が低下する。一方、クロム酸化物付着量がクロム換算
で30mg/m2 を超えると、溶接性が低下する。The amount of tin deposited during the second layer plating of the present invention is
In terms of metallic tin, (1000 / X) + 50mg / m 2 to (30000 / X) +50
It is within the range of mg / m 2 . The amount of tin deposited is (1
If it is less than 000 / X) +50 mg / m 2 , an alloy of metallic tin and steel is formed by the heat at the time of baking the paint, and as a result, metallic tin is reduced and the weldability becomes insufficient. On the other hand, when the amount of deposited tin exceeds (30000 / X) + 50 mg / m 2 in terms of metallic tin,
Metallic tin remains unnecessarily, which is economically disadvantageous. For this reason, the amount of tin deposited during the second layer plating is limited. Also, the amount of chromium oxide deposited in the second layer should be within the range of 1 to 30 mg / m 2 in terms of chromium. If the amount of chromium oxide adhered is less than 1 mg / m 2 in terms of chromium, the corrosion resistance decreases. On the other hand, if the amount of deposited chromium oxide exceeds 30 mg / m 2 in terms of chromium, the weldability will deteriorate.
【００２６】上述した方法によって得られた電解クロメ
ート処理鋼板の塗装加工後の耐食性をさらに向上させる
ためには、第２層の表面上に、１から30mg/m2 の水和ク
ロム酸化物からなるクロメート被膜を形成させても良
い。または、第２層の表面上に公知のクロメート処理を
さらに施して３から30mg/m2 の金属クロムを形成し、さ
らにその上に１から30mg/m2 の水和クロム酸化物からな
るクロメート被膜を形成させても良い。また、同様の目
的のために、次の処理を施してもよい。即ち、0.2 から
5.0g/lの６価のクロムを含む水溶液および／または0.3
から10g/l のポリアクリル酸、アクリルニトリルとイタ
コン酸の共重合体を含む水溶液中に、第１層および第２
層を形成した鋼板を浸漬し、次いで、鋼板に付着した水
溶液を乾燥させる方法である。６価のクロム濃度を、上
述した範囲に限定した理由は、0.2g/l未満では、耐食性
に及ぼす効果が少なく、一方、5.0g/lを超えると塗料密
着性が悪くなるからである。水溶性の樹脂（ポリアクリ
ル酸、アクリルニトリルとイタコン酸の共重合体を含む
水溶液）の含有量（濃度）を、上述した範囲に限定した
理由は、0.3 g/l 未満では、所望の効果が得られず、一
方10g/l を超えると効果が飽和するばかりでなく経済的
でないからである。In order to further improve the corrosion resistance of the electrolytic chromate-treated steel sheet obtained by the above-mentioned method after coating, 1 to 30 mg / m 2 of hydrated chromium oxide is formed on the surface of the second layer. A chromate film may be formed. Alternatively, a known chromate treatment is further applied to the surface of the second layer to form 3 to 30 mg / m 2 of metallic chromium, and a chromate coating consisting of 1 to 30 mg / m 2 of hydrated chromium oxide is further formed thereon. May be formed. Further, the following processing may be performed for the same purpose. That is, from 0.2
Aqueous solution containing 5.0g / l hexavalent chromium and / or 0.3
To 10 g / l of polyacrylic acid, an aqueous solution containing a copolymer of acrylonitrile and itaconic acid, the first layer and the second layer
It is a method of immersing a steel sheet on which a layer is formed and then drying the aqueous solution attached to the steel sheet. The reason why the hexavalent chromium concentration is limited to the above range is that if it is less than 0.2 g / l, the effect on the corrosion resistance is small, and if it exceeds 5.0 g / l, the coating adhesion becomes poor. The reason for limiting the content (concentration) of the water-soluble resin (polyacrylic acid, an aqueous solution containing a copolymer of acrylonitrile and itaconic acid) to the above range is that the desired effect is obtained when the content is less than 0.3 g / l. If not, on the other hand, if it exceeds 10 g / l, the effect is saturated and it is not economical.
【００２７】この発明においては、更に、光沢のある金
属クロム上のクロム酸化物含有錫めっき層を得るため
に、第２層めっき浴の水溶液中にナフチル基にオキシエ
チレン鎖（ [CH2 CH2 O −] n ）の付加したノニオン系
界面活性剤を、1 〜8 g/l 含有させると良い。界面活性
剤には、多くの種類があるが、この発明においては、ナ
フチル基にオキシエチレン鎖が付加した構造のノニオン
系界面活性剤のみが有効であり、光沢があってむらのな
い外観良好な錫めっきが安定して得られる。原因は不明
確であるが、ナフチル基にオキシエチレン鎖の付加した
構造で、さらに、ナフチル基がスルホン化された構造を
有するイオン系界面活性剤では、安定して外観良好な錫
めっきは得られない。更に、この発明の界面活性剤の含
有量は、１から８g/l とすべきである。界面活性剤の含
有量が、１g/l 未満では、光沢剤の効果が現れず、光沢
のある錫めっきが得られない。一方、含有量が８g/l を
超えると、錫めっき電解効率が急激に減少し、経済的に
不利である。Further, in the present invention, in order to obtain a chromium oxide-containing tin plating layer on glossy metallic chromium, an naphthyl group-containing oxyethylene chain ([CH 2 CH 2 It is preferable that the nonionic surfactant to which O −] n ) is added be contained in an amount of 1 to 8 g / l. There are many types of surfactants, but in the present invention, only nonionic surfactants having a structure in which an oxyethylene chain is added to a naphthyl group are effective and have a glossy and even appearance. Stable tin plating is obtained. The cause is unclear, but an ionic surfactant having a structure in which an oxyethylene chain is added to the naphthyl group and having a structure in which the naphthyl group is sulfonated provides stable tin plating with a good appearance. Absent. Furthermore, the content of surfactants according to the invention should be from 1 to 8 g / l. When the content of the surfactant is less than 1 g / l, the effect of the brightening agent does not appear, and bright tin plating cannot be obtained. On the other hand, if the content exceeds 8 g / l, the tin plating electrolysis efficiency decreases sharply, which is economically disadvantageous.
【００２８】[0028]
【実施例】次に、この発明を実施例および比較例によっ
て、更に詳しく説明する。 〔実施例１〕板厚0.22mmの冷延鋼板に、通常の条件で脱
脂、酸洗を施し、次いで、水洗し、次いで、175g/lの無
水クロム酸に、５g/lのケイフッ化ナトリウムおよび１g
/lの硫酸ナトリウムを添加した、公知のクロムメッキ液
中で、鋼板に、100A/dm 2 の電流密度で陰極電解処理を
施して、100mg/m 2 の金属クロムの第１層を鋼板の表面
上に形成した。その後、20g/l の硫酸クロムおよび８g/
l の硫酸第１錫を添加した60g/l 硫酸溶液中で、鋼板に
45℃、60A/dm 2の条件下で陰極電解処理を施して、150m
g/m 2 の錫および６mg/m 2 のクロム酸化物からなる第
２層を形成し、この発明の範囲内の鋼板の供試体を調製
した。EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. [Example 1] A cold-rolled steel sheet having a thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, then with 175 g / l chromic anhydride, and with 5 g / l sodium silicofluoride and 1 g
In a known chromium plating solution containing 1 / l sodium sulfate, the steel sheet was subjected to cathodic electrolysis treatment at a current density of 100 A / dm 2 , and the first layer of 100 mg / m 2 metallic chromium was applied to the surface of the steel sheet. Formed on. After that, 20g / l chromium sulfate and 8g / l
1 g of stannous sulfate was added to the steel sheet in a 60 g / l sulfuric acid solution.
Cathodic electrolysis is performed under the conditions of 45 ° C and 60 A / dm 2 , and 150 m
A second layer consisting of g / m 2 tin and 6 mg / m 2 chromium oxide was formed to prepare a steel sheet specimen within the scope of the invention.
【００２９】〔実施例２〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、50A/dm 2の電流密度で
陰極電解処理を施して、80 mg/m 2 の金属クロムの第１
層を鋼板の表面上に形成した。その後、15g/l の硫酸ク
ロムおよび８g/l の硫酸第１錫、更に、２g/l の６エト
キシレートαナフトールを添加した60g/l 硫酸溶液中
で、鋼板に45℃、80A/dm 2の条件下で陰極電解処理を施
して、130mg/m 2 の錫および５mg/m 2のクロム酸化物か
らなる第２層を第１層上に形成した。次いで、このよう
にして、第１層および第２層が形成された鋼板を、20g/
l の重クロム酸ナトリウムの水溶液中に１秒間浸漬し、
鋼板に付着した水溶液を乾燥させて、第２層上に３mg/m
2 の水和クロム酸化物の第３層を形成し、この発明の
範囲内の鋼板の供試体を調製した。Example 2 A cold-rolled steel sheet having a plate thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l of chromic anhydride, 5 g / l of a caustic agent. In a well-known chromium plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel plate was subjected to cathodic electrolysis treatment at a current density of 50 A / dm 2 to obtain 80 mg / m 2 of metallic chromium
A layer was formed on the surface of the steel sheet. Then, in a 60 g / l sulfuric acid solution containing 15 g / l of chromium sulfate, 8 g / l of stannous sulfate and 2 g / l of 6-ethoxylate α-naphthol, the steel sheet was treated at 45 ° C and 80 A / dm 2 A cathodic electrolysis treatment was performed under the conditions to form a second layer consisting of 130 mg / m 2 tin and 5 mg / m 2 chromium oxide on the first layer. Then, in this way, the steel plate on which the first layer and the second layer were formed, 20 g /
soak for 1 second in an aqueous solution of sodium dichromate
The aqueous solution adhering to the steel sheet is dried to 3 mg / m on the second layer.
A third layer of hydrated chromium oxide of No. 2 was formed and a steel plate specimen within the scope of this invention was prepared.
【００３０】〔実施例３〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、30A/dm 2の電流密度で
陰極電解処理を施して、120mg/m 2 の金属クロムの第１
層を鋼板の表面上に形成した。その後、15g/l の硫酸ク
ロムおよび10g/l の酸化第１錫、更に、５g/l の６エト
キシレートαナフトールを添加した50g/l 硫酸溶液中
で、鋼板に40℃、100A/dm 2 の条件下で陰極電解処理を
施して、500mg/m 2 の錫および３mg/m 2 のクロム酸化
物からなる第２層を第１層上に形成した。次いで、この
ようにして、第１層および第２層が形成された鋼板を20
g/l の重クロム酸ナトリウムの水溶液中で40℃、５A/dm
2 の条件下で陰極電解処理を施して、第２層上に６mg
/m 2の水和クロム酸化物の第３層を形成し、この発明の
範囲内の鋼板の供試体を調製した。Example 3 A cold-rolled steel sheet having a plate thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l of chromic anhydride, 5 g / l of caustic fluoride. In a well-known chrome plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel plate was subjected to cathodic electrolysis treatment at a current density of 30 A / dm 2 , and 120 mg / m 2 of metallic chromium
A layer was formed on the surface of the steel sheet. Then, in a 50 g / l sulfuric acid solution containing 15 g / l of chromium sulfate, 10 g / l of stannous oxide, and 5 g / l of 6-ethoxylate α-naphthol, the steel sheet was treated at 40 ° C. and 100 A / dm 2 A cathodic electrolysis treatment was performed under the conditions to form a second layer consisting of 500 mg / m 2 tin and 3 mg / m 2 chromium oxide on the first layer. Then, in this way, the steel sheet on which the first layer and the second layer are formed is used.
40 ° C, 5 A / dm in g / l sodium dichromate solution
Subjected to cathodic electrolysis treatment with 2 conditions, 6 mg on the second layer
A third layer of hydrated chromium oxide of / m 2 was formed to prepare a steel plate specimen within the scope of this invention.
【００３１】〔実施例４〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、30A/dm 2の電流密度で
陰極電解処理を施し、次いで、１A/dm 2の電流密度で陽
極電解処理を施し、次いで、30A/dm 2の電流密度で陰極
電解処理を施して、50mg/m 2の突起のある金属クロムの
第１層を鋼板の表面上に形成した。その後、25g/l の硫
酸クロムおよび15g/l の硫酸第１錫、更に、３g/l の６
エトキシレートαナフトールを添加した250g/lフェノー
ルスルホン酸（硫酸換算50g/）溶液中で、鋼板に40℃、
90A/dm 2 の条件下で陰極電解処理を施して、300mg/m
2 の錫および11mg/m 2のクロム酸化物からなる第２層を
第１層上に形成した。次いで、このようにして、第１層
および第２層が形成された鋼板を15g/l の無水クロムお
よび0.3 g/l の硫酸ナトリウムを含有する水溶液中で、
鋼板に45℃、10A/dm 2の条件下で陰極電解処理を施し
て、第２層上に５mg/m 2の金属クロムおよびその上層に
16mg/m 2の水和クロム酸化物の第３層および第４層を形
成し、この発明の範囲内の鋼板の供試体を調製した。Example 4 A cold-rolled steel sheet having a plate thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l of chromic anhydride, 5 g / l of a caustic agent. In a well-known chromium plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel sheet was subjected to cathodic electrolysis treatment at a current density of 30 A / dm 2 , and then anodic electrolysis at a current density of 1 A / dm 2. The treatment was followed by a cathodic electrolysis treatment at a current density of 30 A / dm 2 to form a 50 mg / m 2 protrusive first layer of metallic chromium on the surface of the steel sheet. Then 25 g / l chromium sulphate and 15 g / l stannous sulphate and 3 g / l 6
In a 250 g / l phenolsulfonic acid (50 g / sulfuric acid equivalent) solution containing ethoxylate α-naphthol, apply 40 ° C to the steel plate,
Cathodic electrolysis treatment under the condition of 90A / dm 2 gives 300mg / m 2.
A second layer consisting of 2 tin and 11 mg / m 2 chromium oxide was formed on the first layer. Then, in this way, the steel sheet on which the first layer and the second layer are formed, in an aqueous solution containing 15 g / l of anhydrous chromium and 0.3 g / l of sodium sulfate,
The steel sheet was subjected to cathodic electrolysis under the conditions of 45 ° C and 10 A / dm 2 to obtain 5 mg / m 2 of metallic chromium on the second layer and its upper layer.
A third layer and a fourth layer of 16 mg / m 2 of hydrated chromium oxide were formed and a steel plate specimen within the scope of the present invention was prepared.
【００３２】〔実施例５〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、70A/dm 2の電流密度で
陰極電解処理を施して、110mg/m 2 の金属クロムの第１
層を鋼板の表面上に形成した。その後、10g/l の硫酸ク
ロムおよび10g/l の硫酸第１錫を添加した45g/l 硫酸溶
液中で、鋼板に40℃、70A/dm 2の条件下で陰極電解処理
を施して、170mg/m 2 の錫および４mg/m 2のクロム酸化
物からなる第２層を第１層上に形成した。次いで、この
ようにして、第１層および第２層が形成された鋼板を20
g/l の無水クロム酸の水溶液中に１秒間浸漬し、鋼板に
付着した水溶液を乾燥させて、第２層上に２mg/m 2の水
和クロム酸化物の第３層を形成し、この発明の範囲内の
鋼板の供試体を調製した。Example 5 A cold-rolled steel sheet having a plate thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l of chromic anhydride, 5 g / l of a caustic agent. In a well-known chrome plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel plate was subjected to cathodic electrolysis treatment at a current density of 70 A / dm 2 and 110 mg / m 2 of metallic chromium
A layer was formed on the surface of the steel sheet. Then, in a 45g / l sulfuric acid solution containing 10g / l chromium sulphate and 10g / l stannous sulphate added, the steel sheet was subjected to cathodic electrolysis at 40 ° C and 70A / dm 2 to give 170mg / l. the second layer of chromium oxide of tin and 4 mg / m 2 of m 2 was formed on the first layer. Then, in this way, the steel sheet on which the first layer and the second layer are formed is used.
Immerse in an aqueous solution of g / l chromic anhydride for 1 second and dry the aqueous solution adhering to the steel sheet to form a third layer of 2 mg / m 2 of hydrated chromium oxide on the second layer. A steel plate specimen within the scope of the invention was prepared.
【００３３】〔比較例１〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、100A/dm 2 の電流密度
で陰極電解処理を施して、100mg/m 2 の金属クロムの第
１層を鋼板の表面上に形成した。その後、20g/l の硫酸
クロムおよび40g/l の硫酸第１錫を添加した60g/l 硫酸
溶液中で、鋼板に45℃、70A/dm 2の条件下で陰極電解処
理を施して、300mg/m 2 の錫および９mg/m2のクロム酸
化物からなる第２層を形成し、この発明の範囲外の鋼板
の供試体を調製した。[Comparative Example 1] A cold-rolled steel sheet having a thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l chromic anhydride, 5 g / l of a caustic fluoride. The first layer of 100 mg / m 2 metallic chromium was obtained by subjecting the steel sheet to cathodic electrolysis at a current density of 100 A / dm 2 in a known chromium plating solution to which sodium chloride and 1 g / l sodium sulfate were added. Was formed on the surface of the steel sheet. Then, in a 60g / l sulfuric acid solution containing 20g / l chromium sulfate and 40g / l stannous sulfate added, the steel sheet was subjected to cathodic electrolysis treatment at 45 ° C and 70A / dm 2 to give 300mg / l. forming a second layer of chromium oxide of tin and 9 mg / m 2 of m 2, and to prepare a specimen of the outside of the steel plate of the present invention.
【００３４】〔比較例２〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、50A/dm 2の電流密度で
陰極電解処理を施して、80 mg/m 2 の金属クロムの第１
層を鋼板の表面上に形成した。その後、15g/l の硫酸ク
ロムおよび12g/l の硫酸第１錫、更に、２g/l の６エト
キシレートαナフトールを添加した30g/l 硫酸溶液中
で、鋼板に45℃、60A/dm 2の条件下で陰極電解処理を施
して、200mg/m 2 の錫および５mg/m 2のクロム酸化物か
らなる第２層を第１層上に形成した。次いで、このよう
にして、第１層および第２層が形成された鋼板を20g/l
の重クロム酸ナトリウムの水溶液中に１秒間浸漬し、鋼
板に付着した水溶液を乾燥させて、第２層上に３mg/m
2 の水和クロム酸化物の第３層を形成し、この発明の
範囲外の鋼板の供試体を調製した。Comparative Example 2 A cold-rolled steel sheet having a plate thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l of chromic anhydride, 5 g / l of caustic fluoride. In a well-known chromium plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel plate was subjected to cathodic electrolysis treatment at a current density of 50 A / dm 2 to obtain 80 mg / m 2 of metallic chromium
A layer was formed on the surface of the steel sheet. Then, in a 30 g / l sulfuric acid solution containing 15 g / l of chromium sulfate, 12 g / l of stannous sulfate and 2 g / l of 6-ethoxylate α-naphthol, the steel plate was treated at 45 ° C. and 60 A / dm 2 . A cathodic electrolysis treatment was performed under the conditions to form a second layer of 200 mg / m 2 tin and 5 mg / m 2 chromium oxide on the first layer. Then, in this way, the steel sheet on which the first layer and the second layer were formed was 20 g / l.
Dipped in the aqueous solution of sodium dichromate for 1 second to dry the aqueous solution adhering to the steel plate, and 3 mg / m 2 on the second layer.
A third layer of hydrated chromium oxide of No. 2 was formed to prepare a steel plate specimen outside the scope of the present invention.
【００３５】〔比較例３〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、30A/dm 2の電流密度で
陰極電解処理を施して、120mg/m 2 の金属クロムの第１
層を鋼板の表面上に形成した。その後、15g/l の硫酸ク
ロムおよび８g/l の酸化第１錫を添加した60g/l 硫酸溶
液中で、鋼板に45℃、40A/dm 2の条件下で陰極電解処理
を施して、150mg/m 2 の錫および３mg/m 2 のクロム酸
化物からなる第２層を第１層上に形成した。次いで、こ
のようにして、第１層および第２層が形成された鋼板を
20g/l の無水クロム酸および0.3g/lの硫酸ナトリウムの
水溶液中で、鋼板に40℃、10A/dm 2 の条件下で陰極電
解処理を施して、第２層上に４mg/m 2の金属クロム層お
よび10mg/m 2の水和クロム酸化物からなる第３層を形成
し、この発明の範囲外の鋼板の供試体を調製した。Comparative Example 3 A cold-rolled steel sheet having a plate thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l of chromic anhydride, 5 g / l of caustic fluoride. In a well-known chrome plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel plate was subjected to cathodic electrolysis treatment at a current density of 30 A / dm 2 , and 120 mg / m 2 of metallic chromium
A layer was formed on the surface of the steel sheet. Then, in a 60g / l sulfuric acid solution containing 15g / l chromium sulfate and 8g / l stannous oxide added, the steel sheet was subjected to cathodic electrolysis treatment at 45 ° C and 40A / dm 2 to obtain 150mg / l. the second layer of chromium oxide of tin and 3 mg / m 2 of m 2 was formed on the first layer. Then, in this way, the steel sheet on which the first layer and the second layer are formed
The steel sheet was subjected to cathodic electrolysis in an aqueous solution of 20 g / l chromic anhydride and 0.3 g / l sodium sulfate at 40 ° C. and 10 A / dm 2 , and 4 mg / m 2 on the second layer. A metallic chromium layer and a third layer consisting of 10 mg / m 2 of hydrated chromium oxide were formed to prepare a steel plate specimen outside the scope of the present invention.
【００３６】〔比較例４〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、30A/dm 2の電流密度で
陰極電解処理を施て、100mg/m 2 の金属クロムの第１層
を鋼板の表面上に形成した。その後、25g/l の硫酸クロ
ムおよび10g/l の硫酸第１錫、更に、３g/l の６エトキ
シレートαナフトールを添加した250g/lフェノールスル
ホン酸（硫酸換算50g/）溶液中で、鋼板に45℃、160A/d
m 2 の条件下で陰極電解処理を施して、錫およびクロム
酸化物からなる第２層を第１層上に形成し、この発明の
範囲外の鋼板の供試体を調製した。この時の第２層表面
は、部分的にめっきが付着したむらのある表面を呈して
いた[Comparative Example 4] A cold-rolled steel sheet having a thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l chromic anhydride, 5 g / l of caustic fluoride. A first layer of 100 mg / m 2 of metallic chromium was obtained by subjecting a steel sheet to cathodic electrolysis at a current density of 30 A / dm 2 in a known chromium plating solution to which sodium chloride and 1 g / l of sodium sulfate were added. Was formed on the surface of the steel sheet. Then, in a 250g / l phenolsulfonic acid (50g / sulfuric acid equivalent) solution containing 25g / l of chromium sulfate, 10g / l of stannous sulfate and 3g / l of 6-ethoxylate α-naphthol added to the steel sheet. 45 ℃, 160A / d
Cathodic electrolysis was performed under the condition of m 2 to form a second layer composed of tin and chromium oxide on the first layer, and a steel sheet specimen outside the scope of the present invention was prepared. At this time, the surface of the second layer had an uneven surface with partial plating.
【００３７】〔比較例５〕板厚0.22mmの冷延鋼板に、通
常の条件で脱脂、酸洗を施し、次いで、水洗し、次い
で、175g/lの無水クロム酸に、５g/l のケイフッ化ナト
リウムおよび１g/lの硫酸ナトリウムを添加した、公知
のクロムメッキ液中で、鋼板に、70A/dm 2の電流密度で
陰極電解処理を施して、100mg/m 2 の金属クロムの第１
層を鋼板の表面上に形成した。その後、10g/l の硫酸ク
ロムおよび10g/l の硫酸第１錫、更に、２g/l の６エト
キシレートαナフトールスルホン酸を添加した60g/l 硫
酸溶液中で、鋼板に40℃、60A/dm 2の条件下で陰極電解
処理を施して、200mg/m 2 の錫および４mg/m 2のクロム
酸化物からなる第２層を第１層上に形成した。次いで、
このようにして、第１層および第２層が形成された鋼板
を20g/l の無水クロム酸および0.3g/lの硫酸ナトリムの
水溶液中で、鋼板に40℃、10A/dm 2の条件下で陰極電解
処理を施して、４mg/m 2の金属クロム層と10mg/m 2の水
和クロム酸化物からなる第３層を形成し、この発明の範
囲外の鋼板の供試体を調製した。[Comparative Example 5] A cold-rolled steel sheet having a thickness of 0.22 mm was degreased and pickled under normal conditions, then washed with water, and then with 175 g / l chromic anhydride, 5 g / l of caustic fluoride. In a well-known chromium plating solution to which sodium chloride and 1 g / l sodium sulfate were added, the steel sheet was subjected to cathodic electrolysis treatment at a current density of 70 A / dm 2 to obtain 100 mg / m 2 of metallic chromium
A layer was formed on the surface of the steel sheet. Then, in a 60g / l sulfuric acid solution containing 10g / l of chromium sulfate, 10g / l of stannous sulfate and 2g / l of 6-ethoxylate-α-naphtholsulfonic acid, the steel sheet was heated at 40 ° C and 60A / dm subjected to cathodic electrolysis treatment with 2 conditions, to form a second layer of chromium oxide of tin and 4 mg / m 2 of 200 mg / m 2 on the first layer. Then
In this way, the steel sheet on which the first and second layers were formed was immersed in an aqueous solution of 20 g / l chromic anhydride and 0.3 g / l sodium sulphate at 40 ° C. and 10 A / dm 2 conditions. Was subjected to cathodic electrolysis treatment to form a 4 mg / m 2 metallic chromium layer and a 10 mg / m 2 hydrated chromium oxide third layer, and a steel plate specimen outside the scope of the present invention was prepared.
【００３８】以上のようにして調製された供試体の各々
から試験片を切り出し、下記に示す評価を行った。ま
た、処理終了後の第２層のめっきについても、下記に示
す評価を実施した。その結果を、表１に示す。Test pieces were cut out from each of the test pieces prepared as described above, and the following evaluations were performed. In addition, the following evaluation was performed on the plating of the second layer after the treatment. The results are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】(1) 第２層めっき密着性の評価 ティッシュペーパーを用いて、軽く供試体の表面を擦っ
た後、ティッシュペーパーにめっき剥離による汚れが認
められるか、認められないかで評価した。 ○：ティッシュペーパーに汚れが認められない、 ×：ティッシュペーパーに汚れが認められる。(1) Evaluation of Second Layer Plating Adhesion After lightly rubbing the surface of the test piece with a tissue paper, evaluation was made based on whether stains due to plating peeling were observed or not on the tissue paper. ◯: No stain was found on the tissue paper, ×: Soil was found on the tissue paper.
【００４１】(2) めっき外観評価 目視判定を行った。 ○：外観良好（色調均一でむらが認められない）、 ×：外観むらが認められる。(2) Evaluation of plating appearance Visual judgment was performed. ◯: Good appearance (uniform color tone and no unevenness), ×: uneven appearance is observed.
【００４２】(3) 第２層めっき液の安定性 各第２層めっき条件で、５時間の連続処理を行い、その
後、第２層めっき液を一定量サンプリングした後、スラ
ッジを濾過して乾燥後に重量を測定し、錫めっき液中の
スラッジ濃度を定量した。 ○：スラッジ濃度 0.3g/l以下、 △：スラッジ濃度 0.3 超〜0.5g/l未満、 ×：スラッジ濃度 0.5g/l以上。(3) Stability of Second Layer Plating Solution Under each second layer plating condition, continuous treatment was carried out for 5 hours, and then a certain amount of the second layer plating solution was sampled, and then sludge was filtered and dried. After that, the weight was measured to quantify the sludge concentration in the tin plating solution. ○: Sludge concentration of 0.3 g / l or less, △: Sludge concentration of more than 0.3 to less than 0.5 g / l, ×: Sludge concentration of 0.5 g / l or more.
【００４３】表１から明らかなように、比較例１〜５
は、いずれも、めっきの密着性、錫めっき外観および錫
めっき液の安定性のうちのいずれかが悪かった。これに
対して、実施例１〜５は、いずれも、めっきの密着性に
優れ、めっき外観もよく、更に、錫めっき液の安定性に
優れていた。このようなことから、この発明の製造方法
によれば、鋼板の表面上の第１層としての金属クロム層
上に金属錫およびクロム酸化物からなる第２層を形成す
るめっき処理において、めっきの密着性に優れ、むらの
無い良好な表面外観を有するめっき層が得られることが
分かる。さらに、錫スラッジ生成を抑制できることか
ら、めっき浴の劣化防止に有用であることが分かる。As is clear from Table 1, Comparative Examples 1-5
In each case, any of the adhesion of plating, the appearance of tin plating, and the stability of the tin plating solution was poor. On the other hand, in each of Examples 1 to 5, the plating adhesion was excellent, the plating appearance was good, and the stability of the tin plating solution was excellent. From the above, according to the manufacturing method of the present invention, in the plating treatment for forming the second layer made of metallic tin and chromium oxide on the metallic chromium layer as the first layer on the surface of the steel plate, It can be seen that a plating layer having excellent adhesion and a good surface appearance without unevenness can be obtained. Furthermore, since it is possible to suppress the formation of tin sludge, it is found that it is useful for preventing the deterioration of the plating bath.
【００４４】[0044]
【発明の効果】以上説明したように、この発明の製造方
法によれば、めっき密着性の良好な、むらの無い外観良
好な電解処理クロメート処理鋼板が得られるとともに、
更に、錫イオンを含有するめっき液中の錫スラッジの生
成が抑制され、かくして、工業上有用な効果がもたらさ
れる。As described above, according to the manufacturing method of the present invention, it is possible to obtain an electrolytically treated chromate-treated steel sheet having good plating adhesion and good appearance without unevenness.
Further, the generation of tin sludge in the plating solution containing tin ions is suppressed, and thus the industrially useful effect is brought about.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 渡辺 豊文 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toyofumi Watanabe 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Steel Pipe Co., Ltd.
Claims (4)
板の少なくとも一方の表面上に30から300mg/ m2 の範囲
内の付着量の金属クロムからなる第１層を形成し、次い
で、前記第１層が形成された鋼板を水洗し、次いで、水
洗後直ちに、前記第１層が形成された鋼板に対して、5
から50g/l の範囲内の硫酸クロムおよび3 から15g/l の
範囲内の錫(Sn)イオンを含有し、硫酸換算で45から120
g/l の範囲内の酸濃度の水溶液中において、50A/dm2 超
150A/dm 2 以下の範囲内の電流密度によって陰極電解処
理を施すことにより、前記第１層の表面上に、金属錫換
算で(1000/X)＋50から(30000/X) ＋50mg/m2 ( 但し、X
は、前記第１層中の金属クロム付着量である）の範囲内
の付着量の錫およびクロム換算で２から30mg/m2 の範囲
内の付着量のクロム酸化物からなる第２層を形成するこ
とにより、前記水溶液からなるめっき浴の劣化を抑制す
るとともに、前記第１層の表面上に、密着性に優れ、む
らのない良好な表面外観を有する前記第２層を形成する
ことを特徴とする耐食性および溶接性に優れた電解クロ
メート処理鋼板の製造方法。1. A steel sheet is electrochromed to form a first layer of deposited chromium on at least one surface of the steel sheet in an amount of 30 to 300 mg / m 2 ; The steel sheet on which the first layer has been formed is washed with water, and immediately after washing with water, the steel sheet on which the first layer has been formed is
To 50 to 50 g / l chromium sulphate and 3 to 15 g / l tin (Sn) ion, 45 to 120 in terms of sulfuric acid.
Over 50 A / dm 2 in aqueous solutions with acid concentrations in the g / l range.
By performing cathodic electrolysis treatment with a current density within the range of 150 A / dm 2 or less, (1000 / X) +50 to (30000 / X) +50 mg / m 2 (in terms of metallic tin) on the surface of the first layer ( However, X
Is the amount of chromium metal deposited in the first layer) and forms a second layer consisting of an amount of tin in the range of 2 and 30 mg / m 2 of chromium oxide in terms of chromium. By so doing, it is possible to suppress the deterioration of the plating bath made of the aqueous solution and form the second layer on the surface of the first layer, which has excellent adhesion and has a good surface appearance without unevenness. And a method for producing an electrolytic chromate-treated steel sheet having excellent corrosion resistance and weldability.
の範囲内の付着量の水和酸化物からなるクロメート被膜
を形成することを特徴とする、請求項１記載の耐食性お
よび溶接性に優れた電解クロメート処理鋼板の製造方
法。2. On the surface of said second layer 1 to 30 mg / m 2
The method for producing an electrolytic chromate-treated steel sheet having excellent corrosion resistance and weldability according to claim 1, characterized in that a chromate film made of a hydrated oxide having an adhesion amount within the range is formed.
の範囲内の付着量の金属クロム層を形成し、次いで、前
記金属クロム層の表面上に、１から30mg/m2 の付着量の
水和酸化物からなるクロメート被膜を形成することを特
徴とする、請求項１記載の耐食性および溶接性に優れた
電解クロメート処理鋼板の製造方法。3. On the surface of said second layer, 3 to 30 mg / m 2
And forming a chromium chrome coating film comprising a hydrated oxide in an amount of 1 to 30 mg / m 2 on the surface of the metal chromium layer. The method for producing an electrolytic chromate-treated steel sheet having excellent corrosion resistance and weldability according to claim 1.
チレン鎖の付加したノニオン系界面活性剤を1 〜8 g/l
含有させることを特徴とする請求項１、２または３記載
の耐食性および溶接性に優れた電解クロメート処理鋼板
の製造方法。4. The aqueous solution contains 1 to 8 g / l of a nonionic surfactant having an oxyethylene chain added to a naphthyl group.
The method for producing an electrolytic chromate-treated steel sheet having excellent corrosion resistance and weldability according to claim 1, 2 or 3, wherein the steel sheet is contained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03254453A JP3136693B2 (en) | 1991-09-06 | 1991-09-06 | Method for producing electrolytic chromated steel sheet with excellent corrosion resistance and weldability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03254453A JP3136693B2 (en) | 1991-09-06 | 1991-09-06 | Method for producing electrolytic chromated steel sheet with excellent corrosion resistance and weldability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0565698A true JPH0565698A (en) | 1993-03-19 |
| JP3136693B2 JP3136693B2 (en) | 2001-02-19 |
Family
ID=17265228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03254453A Expired - Fee Related JP3136693B2 (en) | 1991-09-06 | 1991-09-06 | Method for producing electrolytic chromated steel sheet with excellent corrosion resistance and weldability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136693B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06346253A (en) * | 1993-06-11 | 1994-12-20 | Hitachi Cable Ltd | Metallic strip for tube making and metallic tube and cable using the strip |
| JP2009235456A (en) * | 2008-03-26 | 2009-10-15 | Okuno Chem Ind Co Ltd | Solution for use in electrolytically treating trivalent-chromium plated film |
-
1991
- 1991-09-06 JP JP03254453A patent/JP3136693B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06346253A (en) * | 1993-06-11 | 1994-12-20 | Hitachi Cable Ltd | Metallic strip for tube making and metallic tube and cable using the strip |
| JP2009235456A (en) * | 2008-03-26 | 2009-10-15 | Okuno Chem Ind Co Ltd | Solution for use in electrolytically treating trivalent-chromium plated film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3136693B2 (en) | 2001-02-19 |
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