JP3331794B2 - Surface-treated steel sheet having zinc-based plating film and excellent in white rust resistance and method for producing the same - Google Patents
Surface-treated steel sheet having zinc-based plating film and excellent in white rust resistance and method for producing the sameInfo
- Publication number
- JP3331794B2 JP3331794B2 JP33376794A JP33376794A JP3331794B2 JP 3331794 B2 JP3331794 B2 JP 3331794B2 JP 33376794 A JP33376794 A JP 33376794A JP 33376794 A JP33376794 A JP 33376794A JP 3331794 B2 JP3331794 B2 JP 3331794B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- steel sheet
- white rust
- treated steel
- rust resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は亜鉛系めっき皮膜を有す
る耐白錆性に優れた表面処理鋼板及びその製造方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel sheet having a zinc-based plating film and having excellent white rust resistance and a method for producing the same.
【０００２】[0002]
【従来の技術】亜鉛系めっき鋼板は耐食性に優れている
ため、近年その適用分野が著しく拡大しているが、この
種のめっき鋼板は白錆が発生し易いという欠点がある。
従来、亜鉛系めっき鋼板の白錆を防止するための表面処
理法としては、クロメート系防食剤による処理が広く行
われている。しかし、近年、クロム酸等による人体への
悪影響や環境破壊等が大きな問題となっていることか
ら、クロメート処理工程の管理、廃水処理等にも大きな
制約が生じており、また、クロメート処理物による二次
汚染も問題化している。このため、近年、クロメート系
防食剤に代わる防食剤の検討が盛んに行われている。2. Description of the Related Art Galvanized steel sheets have been widely used in recent years because of their excellent corrosion resistance. However, such coated steel sheets have a drawback that white rust is easily generated.
BACKGROUND ART Conventionally, as a surface treatment method for preventing white rust of a zinc-based plated steel sheet, treatment with a chromate-based anticorrosive has been widely performed. However, in recent years, adverse effects on the human body and environmental destruction due to chromic acid and the like have become serious problems, and thus there are great restrictions on the management of the chromate treatment process, wastewater treatment, and the like. Secondary pollution has also become a problem. For this reason, in recent years, anticorrosive agents instead of chromate-based anticorrosive agents have been actively studied.
【０００３】[0003]
【発明が解決しようとする課題】クロメート処理に代わ
る防食方法としては、フィチン酸を主成分とする処理剤
による処理方法（特公昭４８−４３４０６号）、タンニ
ン酸による処理方法（特公昭５１−２９０２号）等が知
られている。しかし、これらの処理方法は無処理の場合
に比べて確かに耐食性は向上するもののその耐食性は十
分なものではなく、また、処理によってめっき面が着色
されるため外観が劣る、処理剤のコストが高い等の欠点
がある。As an alternative to the chromate treatment, anticorrosion methods include a treatment method using a phytic acid-based treating agent (JP-B-48-43406) and a treatment method using tannic acid (JP-B-51-2902). No.) etc. are known. However, although these treatment methods certainly improve the corrosion resistance as compared to the case of no treatment, the corrosion resistance is not sufficient, and the plating surface is colored by the treatment, the appearance is inferior, the cost of the treatment agent is low. There are drawbacks such as high.
【０００４】また、他の処理方法として、有機硫黄化合
物を含む防食剤による表面処理方法が知られている。有
機硫黄化合物は元々金属のインヒビターとして使用され
ており、金属表面に配位あるいは吸着し、腐食反応を抑
制して防食作用をする。例えば、特公昭５９−４８８６
７号にはメルカプト基を有する７員環のω-チオカプロ
ラクタムを用いた処理法が、また、特開昭５７−１９８
２６７号には、メルカプト基を有する複素環化合物とタ
ンニン酸とを複合させた処理液による処理法がそれぞれ
開示されている。しかし、これらの方法で用いる処理液
はコストが高いばかりでなく、前者の処理法では耐白錆
性が十分でなく、また、後者の処理法ではめっき面が着
色され、しかも処理液管理が難しい等、実用化には問題
が多い。[0004] As another treatment method, a surface treatment method using an anticorrosive containing an organic sulfur compound is known. The organic sulfur compound is originally used as a metal inhibitor, and coordinates or adsorbs on the metal surface to suppress a corrosion reaction and to perform an anticorrosion action. For example, Japanese Patent Publication No. 59-4886
No. 7 discloses a treatment method using a 7-membered ω-thiocaprolactam having a mercapto group, and JP-A-57-198.
No. 267 discloses a treatment method using a treatment solution in which a heterocyclic compound having a mercapto group and tannic acid are combined. However, the processing solutions used in these methods are not only expensive, but the former processing method does not have sufficient white rust resistance, and the latter processing method causes the plating surface to be colored, and the processing liquid management is difficult. There are many problems for practical use.
【０００５】本発明はこのような従来の問題に鑑み、優
れた耐白錆性を有するとともに、低コストで且つ簡易に
製造でき、しかも、製造の際に特別な廃水処理対策を必
要としない亜鉛系めっき皮膜を有する表面処理鋼板及び
その製造方法の提供を目的とする。In view of the above problems, the present invention has excellent white rust resistance, can be manufactured easily at low cost, and requires no special wastewater treatment measures at the time of manufacture. An object of the present invention is to provide a surface-treated steel sheet having a system plating film and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】このような目的を達成す
るための本発明の構成は以下の通りである。 (1) 亜鉛系めっき皮膜の上に、複素環構造を有し、メル
カプト基を３個以上有する有機硫黄化合物を含む皮膜を
有することを特徴とする亜鉛系めっき皮膜を有する耐白
錆性に優れた表面処理鋼板。The structure of the present invention for achieving the above object is as follows. (1) A zinc-based plating film having a heterocyclic structure and containing an organic sulfur compound having three or more mercapto groups on the zinc-based plating film, and having excellent white rust resistance. Surface treated steel sheet.
【０００７】(2) 上記(1)の表面処理鋼板において、有
機硫黄化合物がトリチオシアヌル酸であることを特徴と
する亜鉛系めっき皮膜を有する耐白錆性に優れた表面処
理鋼板。 (3) 亜鉛系めっき鋼板の表面に、複素環構造を有し、メ
ルカプト基を３個以上有する有機硫黄化合物を含み、ｐ
Ｈが１．５以上４．５以下である水溶液を塗布した後乾
燥させるか若しくは亜鉛系めっき鋼板を前記水溶液中に
浸漬した後乾燥させることを特徴とする、亜鉛系めっき
皮膜を有する耐白錆性に優れた表面処理鋼板の製造方
法。(2) The surface-treated steel sheet according to the above (1), wherein the organic sulfur compound is trithiocyanuric acid and has a zinc-based plating film and is excellent in white rust resistance. (3) The surface of a galvanized steel sheet contains an organic sulfur compound having a heterocyclic structure and having three or more mercapto groups,
A white rust-resistant zinc-coated plating film, characterized in that an aqueous solution having H of 1.5 or more and 4.5 or less is applied and dried, or a zinc-based plated steel sheet is immersed in the aqueous solution and then dried. For producing surface-treated steel sheets with excellent heat resistance.
【０００８】[0008]
【作用】本発明は、配位や吸着等による化学結合性が高
い有機硫黄化合物の中で、特に、複素環構造を有し且つ
メルカプト基（ＳＨ基）を３個以上有する有機硫黄化合
物が、亜鉛系めっき鋼板の耐白錆性に優れた効果を発揮
することを見出しなされたものである。複素環構造を有
し、メルカプト基を３個以上有する有機硫黄化合物は下
記の一般式で表される。According to the present invention, among organic sulfur compounds having high chemical bonding property by coordination and adsorption, etc., in particular, an organic sulfur compound having a heterocyclic structure and having three or more mercapto groups (SH groups), It has been found that a galvanized steel sheet exhibits an excellent effect on white rust resistance. An organic sulfur compound having a heterocyclic structure and having three or more mercapto groups is represented by the following general formula.
【化１】 （式中Ｘ、Ｙ、ＺはＲ1ＳＨを表し、Ｒ1はＣＮ、ＣＮ−
Ｒ2−ＳＨ、アルキル基であり、Ｒ2はアルキル基または
アミド基である）Embedded image (Where X, Y, and Z represent R 1 SH, and R 1 is CN, CN-
R 2 —SH is an alkyl group, and R 2 is an alkyl group or an amide group)
【０００９】このような有機硫黄化合物としては、トリ
チオホルムアルデヒド、トリチオシアヌル酸、2-チオブ
チル-4,6-ジチオトリアジン、2-チオアミド-4,6-ジチオ
トリアジン等を挙げることができる。例えば、上記トリ
チオシアヌル酸は下記の構造式で表される。Examples of such organic sulfur compounds include trithioformaldehyde, trithiocyanuric acid, 2-thiobutyl-4,6-dithiotriazine, 2-thioamide-4,6-dithiotriazine and the like. For example, the above trithiocyanuric acid is represented by the following structural formula.
【化２】 Embedded image
【００１０】本発明の表面処理鋼板は、亜鉛系めっき皮
膜の上層に上述した特定の有機硫黄化合物を含有した皮
膜が形成され、これにより極めて優れた耐白錆性を示
す。本発明の表面処理鋼板がこのような高い耐白錆性を
示す理由は必ずしも明らかではないが、この特性は以下
のようなメカニズムにより得られるものと考えられる。
すなわち、亜鉛系めっき皮膜の上層に形成される皮膜中
に複素環構造を有し且つメルカプト基を３個以上有する
有機硫黄化合物が含まれている場合、１個または２個の
メルカプト基が鋼板にめっきされた亜鉛上に吸着され、
その分子１個あたりの被覆面積が大きいために分子レベ
ルで高い被覆率が得られ、しかも残りのメルカプト基が
他のメルカプト基と架橋して平面方向のネットワークを
形成する。この結果、亜鉛系めっき表面にメルカプト基
の３次元的な緻密なネットワークが形成され、極めて高
い防食効果（耐白錆性）が得られるものと考えられる。
これに対し、先に述べた特公昭５９−４８８６７号に開
示されたω−チオカプロラクタムは１個のメルカプト基
を有するチオール誘導体であるため、上記のような作用
が得られず、十分な耐白錆性が得られないものと考えら
れる。In the surface-treated steel sheet of the present invention, a film containing the above-mentioned specific organic sulfur compound is formed on the zinc-based plating film, thereby exhibiting extremely excellent white rust resistance. Although the reason why the surface-treated steel sheet of the present invention exhibits such high white rust resistance is not necessarily clear, it is considered that this property is obtained by the following mechanism.
That is, when an organic sulfur compound having a heterocyclic structure and having three or more mercapto groups is contained in the film formed on the zinc-based plating film, one or two mercapto groups are added to the steel sheet. Adsorbed on plated zinc,
Since the coating area per molecule is large, a high coverage is obtained at a molecular level, and the remaining mercapto groups crosslink with other mercapto groups to form a planar network. As a result, it is considered that a three-dimensional dense network of mercapto groups is formed on the zinc-based plating surface, and an extremely high anticorrosion effect (white rust resistance) is obtained.
On the other hand, the above-mentioned ω-thiocaprolactam disclosed in JP-B-59-48867 is a thiol derivative having one mercapto group, so that the above-mentioned action cannot be obtained and sufficient whitening resistance is not obtained. It is considered that rust property cannot be obtained.
【００１１】皮膜中に含まれる有機硫黄化合物として
は、先の挙げたものの中でも特に、水溶液としての取り
扱いが容易で且つ安価でもあるトリチオシアヌル酸が最
も実用的であり、この有機硫黄化合物を含む皮膜を亜鉛
系めっき鋼板に適用することにより、塩水等の腐食環境
下で極めて強固で緻密なメルカプト基の３次元的ネット
ワークを形成し、鋼板を防食する。As the organic sulfur compound contained in the film, trithiocyanuric acid, which is easy and inexpensive to handle as an aqueous solution, is most practical among the above-mentioned compounds. When applied to a galvanized steel sheet, a very strong and dense three-dimensional network of mercapto groups is formed under a corrosive environment such as salt water, thereby preventing the steel sheet from being corroded.
【００１２】皮膜中の有機硫黄化合物の濃度は特に限定
しないが、皮膜中のメルカプト基のの濃度は０．００１
〜０．０５Ｍ程度とすることが望ましい。メルカプト基
の濃度が０．００１Ｍ未満では本発明が期待する耐白錆
性が十分に得られなくなり、一方、０．０５Ｍを超える
濃度としても添加量に見合う効果が期待できず、経済的
に好ましくない。Although the concentration of the organic sulfur compound in the film is not particularly limited, the concentration of the mercapto group in the film is 0.001.
It is desirable to set it to about 0.05M. If the concentration of the mercapto group is less than 0.001M, the white rust resistance expected by the present invention cannot be sufficiently obtained. On the other hand, even if the concentration exceeds 0.05M, the effect corresponding to the added amount cannot be expected, and it is economically preferable. Absent.
【００１３】めっき皮膜の上層に有機硫黄化合物を含む
皮膜を形成するための処理では、処理剤は非水系の溶
液、水溶液あるいは懸濁液等のいずれの状態で塗布して
もよく、いずれの場合でも優れた耐食性が得られるが、
コスト面からは水溶液を用いるのが最も有利である。ま
た、処理剤（水溶液等）をめっき鋼板面に塗布する方法
としては、浸漬法、ロールコーティング法、スプレー法
等が適用でき、塗布後、必要に応じて熱風加熱、輻射加
熱あるいは誘導加熱等の方法で乾燥される。なお、この
乾燥温度が高過ぎると有機硫黄化合物と亜鉛との結合が
外れて耐白錆性が低下するおそれがあり、このため乾燥
温度は２５０℃以下とすることが好ましい。In the treatment for forming a film containing an organic sulfur compound on the plating film, the treating agent may be applied in any state such as a non-aqueous solution, an aqueous solution or a suspension. But excellent corrosion resistance can be obtained,
It is most advantageous to use an aqueous solution in terms of cost. Further, as a method of applying a treating agent (such as an aqueous solution) to the surface of the plated steel sheet, a dipping method, a roll coating method, a spray method, or the like can be applied. Dried by the method. If the drying temperature is too high, the bond between the organosulfur compound and zinc may be lost and the white rust resistance may be reduced. Therefore, the drying temperature is preferably 250 ° C. or lower.
【００１４】次に、水溶液を用いる本発明の製造法につ
いて説明すると、この製造法では上述した有機硫黄化合
物を含み、且つｐＨが１．５〜４．５に調整された水溶
液を、亜鉛系めっき鋼板の表面に塗布した後乾燥させる
か若しくは亜鉛系めっき鋼板を前記水溶液中に浸漬した
後乾燥させる。優れた防食性を得るためには水溶液のｐ
Ｈを１．５〜４．５に調整することが重要である。水溶
液のｐＨを４．５以下とする理由は、亜鉛系めっき皮膜
の溶解を起こさせることにより、溶出した亜鉛が有機硫
黄化合物の結合していないメルカプト基に吸着して他の
メルカプト基との架橋を誘発させ（つまり、フリーのメ
ルカプト基２個が溶出した亜鉛を介して結合することで
架橋が誘発される）、これによって優れたバリヤ効果を
発現させることにある。水溶液のｐＨが４．５を超える
と上記のような作用効果が十分に得られない。Next, the production method of the present invention using an aqueous solution will be described. In this production method, an aqueous solution containing the above-mentioned organic sulfur compound and having a pH adjusted to 1.5 to 4.5 is coated with zinc-based plating. It is dried after being applied to the surface of the steel sheet, or is immersed in the aqueous solution and then dried. In order to obtain excellent anticorrosion properties, p
It is important to adjust H to 1.5 to 4.5. The reason for adjusting the pH of the aqueous solution to 4.5 or less is that, by causing the dissolution of the zinc-based plating film, the eluted zinc is adsorbed to the mercapto group to which the organic sulfur compound is not bonded, and crosslinked with other mercapto groups. (That is, cross-linking is induced by binding of two free mercapto groups via the eluted zinc), thereby exhibiting an excellent barrier effect. If the pH of the aqueous solution exceeds 4.5, the above-mentioned effects cannot be sufficiently obtained.
【００１５】一方、水溶液のｐＨが１．５未満では、亜
鉛の溶出速度が高いため耐食性は良好であるが、亜鉛溶
出量が多いために処理液中で亜鉛イオンと有機硫黄化合
物がキレート化し、沈殿しやすくなる。以上の理由から
水溶液のｐＨは１．５〜４．５とする。なお、本発明が
対象とする亜鉛系めっき皮膜とは、亜鉛めっき及び鉄−
亜鉛合金めっき等をはじめとする各種亜鉛系合金めっき
を含み、また、最上層に上記亜鉛系めっき層を有する複
層めっき、めっき層中に各種微粒子を分散させた亜鉛系
複合めっき等も含む。On the other hand, when the pH of the aqueous solution is less than 1.5, the corrosion resistance is good due to the high elution rate of zinc, but the zinc ion and the organic sulfur compound are chelated in the treatment liquid due to the large amount of zinc eluted, It is easy to precipitate. For the above reasons, the pH of the aqueous solution is set to 1.5 to 4.5. The zinc-based plating film targeted by the present invention includes zinc plating and iron-
It includes various types of zinc-based alloy plating such as zinc alloy plating, and also includes multi-layer plating having the above-mentioned zinc-based plating layer on the uppermost layer, and zinc-based composite plating in which various fine particles are dispersed in the plating layer.
【００１６】[0016]
〔実施例１〜実施例１９〕板厚０．６ｍｍの電気亜鉛め
っき鋼板（付着量：片面当たり２０ｇ／ｍ2）の表面に
本発明が規定する有機硫黄化合物を含む溶液を種々の方
法で塗布し、乾燥させた。処理液のｐＨは、必要に応じ
て塩酸またはアンモニア水を用いて調整した。これらの
試験片をＪＩＳ Ｚ ２３７１に基づいて塩水噴霧試験に
供し、白錆発生面積率を調べた。その結果を表１〜表３
に示す。[Examples 1 to 19] A solution containing an organic sulfur compound specified by the present invention was applied to the surface of an electrogalvanized steel sheet having a thickness of 0.6 mm (adhesion amount: 20 g / m 2 per side) by various methods. And dried. The pH of the treatment liquid was adjusted using hydrochloric acid or aqueous ammonia as needed. These test pieces were subjected to a salt spray test based on JIS Z2371 to examine a white rust generation area ratio. The results are shown in Tables 1 to 3.
Shown in
【００１７】〔比較例１〜比較例７〕板厚０．６ｍｍの
電気亜鉛めっき鋼板（付着量：片面当たり２０ｇ／
ｍ2）の表面にメルカプト基を１個または２個有する有
機硫黄化合物を含む溶液を種々の方法で塗布し、乾燥さ
せた。これらの試験片と無処理の板厚０．６ｍｍの電気
亜鉛めっき鋼板（付着量：片面当たり２０ｇ／ｍ2）を
ＪＩＳ Ｚ ２３７１に基づいて塩水噴霧試験に供し、白
錆発生面積率を調べた。その結果を表４に示す。なお、
比較例１〜比較例６で用いた各化合物中のメルカプト基
の個数は以下の通りである。 オクタデカンチオール…１個 ベンゼンチオール …１個 ドデカンジチオール …２個Comparative Examples 1 to 7 Electrogalvanized steel sheet having a thickness of 0.6 mm (adhesion amount: 20 g / side / side)
A solution containing an organic sulfur compound having one or two mercapto groups was applied to the surface of m 2 ) by various methods and dried. These test pieces and an untreated electrogalvanized steel sheet having a thickness of 0.6 mm (adhesion amount: 20 g / m 2 per side) were subjected to a salt spray test based on JIS Z 2371, and the area ratio of white rust occurrence was examined. . Table 4 shows the results. In addition,
The number of mercapto groups in each compound used in Comparative Examples 1 to 6 is as follows. Octadecanethiol ... 1 benzenethiol ... 1 dodecanedithiol ... 2
【００１８】表１〜表４よれば、本発明による実施例１
〜１９は比較例１〜７に較べて極めて優れた耐白錆性が
得られていることが判る。According to Tables 1 to 4, Example 1 according to the present invention is shown.
19 shows that extremely excellent white rust resistance was obtained as compared with Comparative Examples 1 to 7.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】[0021]
【表３】 [Table 3]
【００２２】[0022]
【表４】 [Table 4]
【００２３】[0023]
【発明の効果】本願の請求項１の発明に係る亜鉛系めっ
き皮膜を有する表面処理鋼板は、優れた耐白錆性を有す
るとともに、低コストで且つ簡易に製造でき、しかも、
製造の際にクロメート処理の場合のような特別な廃水処
理対策を必要としないという利点がある。本願の請求項
２の発明に係る亜鉛系めっき皮膜を有する表面処理鋼板
は、上記の効果に加えて、製造の際に用いる処理剤が安
価で且つその取扱が容易であるという利点があり、この
ため特に低コストで且つ簡易に製造することができる。
本願の請求項３の発明に係る製造方法は、優れた耐白錆
性を有する表面処理鋼板を低コストで且つ簡易に製造で
き、しかも、クロメート処理の場合のような特別な廃水
処理対策を必要としないという利点がある。The surface-treated steel sheet having a zinc-based plating film according to the invention of claim 1 of the present application has excellent white rust resistance, can be manufactured at low cost and easily, and
There is an advantage that special wastewater treatment measures are not required during the production as in the case of the chromate treatment. The surface-treated steel sheet having the zinc-based plating film according to the invention of claim 2 of the present application has the advantage that, in addition to the above-described effects, the treating agent used in production is inexpensive and easy to handle. Therefore, it can be particularly easily manufactured at low cost.
The production method according to the invention of claim 3 of the present application can produce a surface-treated steel sheet having excellent white rust resistance at low cost and easily, and requires special wastewater treatment measures as in the case of chromate treatment. There is an advantage that it does not.
フロントページの続き (56)参考文献 特開 平７−173679（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23F 11/00 Continuation of the front page (56) References JP-A-7-173679 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23F 11/00
Claims (3)
有し、メルカプト基を３個以上有する有機硫黄化合物を
含む皮膜を有することを特徴とする亜鉛系めっき皮膜を
有する耐白錆性に優れた表面処理鋼板。1. A white rust resistant zinc coating having a heterocyclic structure and containing an organic sulfur compound having three or more mercapto groups on the zinc coating. Excellent surface treated steel sheet.
あることを特徴とする請求項１に記載の亜鉛系めっき皮
膜を有する耐白錆性に優れた表面処理鋼板。2. The surface-treated steel sheet having excellent white rust resistance according to claim 1, wherein the organic sulfur compound is trithiocyanuric acid.
を有し、メルカプト基を３個以上有する有機硫黄化合物
を含み、ｐＨが１．５以上４．５以下である水溶液を塗
布した後乾燥させるか若しくは亜鉛系めっき鋼板を前記
水溶液中に浸漬した後乾燥させることを特徴とする、亜
鉛系めっき皮膜を有する耐白錆性に優れた表面処理鋼板
の製造方法。3. An aqueous solution containing an organic sulfur compound having a heterocyclic structure and having three or more mercapto groups and having a pH of 1.5 or more and 4.5 or less is applied to the surface of a zinc-based plated steel sheet. A method for producing a surface-treated steel sheet having a zinc-based plating film and having excellent white rust resistance, comprising drying or immersing a zinc-based plated steel sheet in the aqueous solution and then drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33376794A JP3331794B2 (en) | 1994-12-19 | 1994-12-19 | Surface-treated steel sheet having zinc-based plating film and excellent in white rust resistance and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33376794A JP3331794B2 (en) | 1994-12-19 | 1994-12-19 | Surface-treated steel sheet having zinc-based plating film and excellent in white rust resistance and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08176857A JPH08176857A (en) | 1996-07-09 |
| JP3331794B2 true JP3331794B2 (en) | 2002-10-07 |
Family
ID=18269733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33376794A Expired - Fee Related JP3331794B2 (en) | 1994-12-19 | 1994-12-19 | Surface-treated steel sheet having zinc-based plating film and excellent in white rust resistance and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3331794B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4939020B2 (en) * | 2005-09-21 | 2012-05-23 | 新光電気工業株式会社 | Electroless plating pretreatment agent comprising S-alkyl substituted triazine thiol derivative and electroless plating method using the same |
-
1994
- 1994-12-19 JP JP33376794A patent/JP3331794B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08176857A (en) | 1996-07-09 |
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