JP2003105587A - Surface treated steel sheet for electronic part, and production method therefor - Google Patents

Surface treated steel sheet for electronic part, and production method therefor

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Publication number
JP2003105587A
JP2003105587A JP2001298098A JP2001298098A JP2003105587A JP 2003105587 A JP2003105587 A JP 2003105587A JP 2001298098 A JP2001298098 A JP 2001298098A JP 2001298098 A JP2001298098 A JP 2001298098A JP 2003105587 A JP2003105587 A JP 2003105587A
Authority
JP
Japan
Prior art keywords
layer
plating
steel sheet
treatment
treated steel
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
Application number
JP2001298098A
Other languages
Japanese (ja)
Other versions
JP4954406B2 (en
Inventor
Hiroyuki Yamane
博之 山根
Takahiro Hayashida
貴裕 林田
Masao Komai
正雄 駒井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Kohan Co Ltd
Original Assignee
Toyo Kohan Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Kohan Co Ltd filed Critical Toyo Kohan Co Ltd
Priority to JP2001298098A priority Critical patent/JP4954406B2/en
Publication of JP2003105587A publication Critical patent/JP2003105587A/en
Application granted granted Critical
Publication of JP4954406B2 publication Critical patent/JP4954406B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a surface treated steel sheet which has excellent solderability, rust resistance, electric conductivity and whisker resistance. SOLUTION: In the surface treated steel sheet, as a lower layer, tinning is present, and as an upper layer, a V-containing layer is present. Alternatively, the steel sheet is subjected to galvanizing as an intermediate layer. Alternatively, the steel sheet is subjected to diffusion treatment by heat treatment. Thus, the surface treated steel sheet having excellent solderability, rust resistance, electric conductivity and whisker resistance is provided.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】この発明は電子部品用表面処
理鋼板及びその製造方法に関する。特に、半田性、耐錆
性及び耐ホイスカ性に優れた電子部品用表面処理鋼板及
びその製造方法に関する。TECHNICAL FIELD The present invention relates to a surface-treated steel sheet for electronic parts and a method for manufacturing the same. In particular, the present invention relates to a surface-treated steel sheet for electronic parts, which has excellent solderability, rust resistance and whisker resistance, and a method for manufacturing the same.

【０００２】[0002]

【従来の技術】一般に電気製品等の電子部品に使用され
る表面処理鋼板として半田付け性が要求される用途には
ぶりきが、半田付け性が要求されない用途にはＺｎめっ
き鋼板が使用され、また、一部では耐錆性、耐ホイスカ
性についても厳しく要求されているものがある。更に、
近年電磁波による誤動作をなくすために、電磁波シール
ド性も要求されるようになった。この電磁波シールド性
は、表面の電気抵抗が小さいことが必要である。このよ
うな状況の中で、ぶりきはホイスカが発生しやすく、長
く延びたこのホイスカが電子部品の回路で短絡を起こす
原因となる。また、Ｚｎめっきはめっきだけでは経時に
よって表面にＺｎの酸化物が形成し、半田性が極端に悪
くなるとという問題がある。さらに、ぶりきおよびＺｎ
めっきは、防錆性を向上させるために、鋼板をクロム酸
塩を含む溶液中で表面処理し、クロメート皮膜などの保
護皮膜を形成させている。クロメート皮膜は電解を伴わ
ない浸漬処理や塗布処理、電解処理などの方法を用いて
鋼板上に形成される。しかし、電解を伴わない浸漬処理
や塗布処理で形成されるクロメート皮膜中には有害な６
価クロムが含有されており、人体や環境に対して好まし
くない影響を与える。また電解処理による電解クロメー
ト皮膜は有害な６価クロムを含む溶液を用いて行われ、
さらに電解中に発生するクロム酸ミストは作業環境に好
ましくない影響を与え得る。2. Description of the Related Art In general, surface-treated steel sheets used for electronic parts such as electric appliances are tinplate for applications requiring solderability and Zn-plated steel sheets for applications not requiring solderability. In addition, there are some where rust resistance and whisker resistance are strictly required. Furthermore,
In recent years, in order to eliminate malfunctions due to electromagnetic waves, electromagnetic wave shielding properties have also been required. This electromagnetic wave shielding property requires that the surface has a low electric resistance. In such a situation, tin whiskers are likely to generate whiskers, and this long whisker causes a short circuit in the circuit of the electronic component. In addition, Zn plating has a problem in that Zn oxide is formed on the surface with the lapse of time only by plating, resulting in extremely poor solderability. In addition, tinplate and Zn
In the plating, in order to improve rust prevention, the steel sheet is surface-treated in a solution containing chromate to form a protective film such as a chromate film. The chromate film is formed on the steel sheet by a method such as dipping treatment, coating treatment, or electrolytic treatment that does not involve electrolysis. However, it is harmful to the chromate film formed by dipping or coating without electrolysis.
It contains valent chromium and has an unfavorable effect on the human body and environment. The electrolytic chromate coating by electrolytic treatment is performed using a solution containing harmful hexavalent chromium,
Furthermore, chromate mist generated during electrolysis can have an unfavorable effect on the working environment.

【０００３】[0003]

【発明が解決しようとする課題】本発明は、半田性、耐
錆性、耐ホイスカ性及びシールド性に優れた電子部品用
表面処理鋼板及びその製造方法を提供することを目的と
する。SUMMARY OF THE INVENTION It is an object of the present invention to provide a surface-treated steel sheet for electronic parts which is excellent in solderability, rust resistance, whisker resistance and shieldability, and a method for producing the same.

【０００４】[0004]

【課題を解決するための手段】本発明によれば、鋼板の
少なくとも片面に、下層としてＳｎめっき４〜１２ｇ／
ｍ２、上層にＶ量が５〜４００ｍｇ／ｍ２の層を有して
いることを特徴とする電子部品用表面処理鋼板が提供さ
れる。本発明の表面処理鋼板では、前記下層と上層との
間に、中間層としてＺｎめっき１０〜１０００ｍｇ／ｍ
２の層を形成することができる。また、本発明によれ
ば、鋼板の少なくとも片面に、下層としてＳｎめっき４
〜１２ｇ／ｍ２の層を形成し、更に上層としてＶ量が５
〜４００ｍｇ／ｍ２の層を形成する電子部品用表面処理
鋼板の製造方法において、前記Ｓｎめっき層（下層）を
形成した後前記Ｖ層（上層）の形成に先だって、又は前
記Ｖ層（上層）を形成した後に、熱処理を施すことを特
徴とする製造方法が提供される。本発明によれば更に、
鋼板の少なくとも片面に、下層としてＳｎめっき４〜１
２ｇ／ｍ２を形成し、次いで中間層としてＺｎめっき１
０〜１０００ｍｇ／ｍ２を形成し、更に上層としてＶ量
が５〜４００ｍｇ／ｍ２の層を形成する電子部品用表面
処理鋼板の製造方法において、前記Ｚｎめっき層（中間
層）を形成した後前記Ｖ層（上層）の形成に先だって、
若しくは前記Ｖ層（上層）を形成した後に、熱処理を施
すことを特徴とする製造方法が提供される。上記の製造
方法において、熱処理は、板温を１５０〜４００℃の範
囲として行なうことが好ましい。According to the present invention, at least one surface of a steel sheet is Sn-plated as a lower layer in an amount of 4 to 12 g /
m 2 and a surface-treated steel sheet for electronic parts, which has a layer with a V content of 5 to 400 mg / m 2 as an upper layer. In the surface-treated steel sheet of the present invention, Zn plating is 10 to 1000 mg / m as an intermediate layer between the lower layer and the upper layer.
Two layers can be formed. Moreover, according to the present invention, at least one surface of the steel sheet is plated with Sn as a lower layer.
~ 12 g / m 2 layer is formed, and V amount is 5 as an upper layer.
In the method for producing a surface-treated steel sheet for electronic parts, which forms a layer of ~ 400 mg / m 2 , after forming the Sn plating layer (lower layer) and before forming the V layer (upper layer), or the V layer (upper layer). A manufacturing method is provided, which comprises performing a heat treatment after forming the. Further according to the invention,
At least one side of the steel sheet, Sn plating 4 ~ 1 as a lower layer
2 g / m 2 formed, then Zn plated as intermediate layer 1
Forming a 0~1000mg / m 2, in yet a method of manufacturing an electronic component for surface treated steel sheet V amount as the upper layer to form a layer of 5 to 400 mg / m 2, after forming the Zn plating layer (intermediate layer) Prior to the formation of the V layer (upper layer),
Alternatively, there is provided a manufacturing method characterized by performing heat treatment after forming the V layer (upper layer). In the above manufacturing method, the heat treatment is preferably performed at a plate temperature in the range of 150 to 400 ° C.

【０００５】[0005]

【発明の実施の形態】以下に、本発明の内容について詳
しく説明する。 ［使用する鋼板］本発明に使用する鋼板としては普通鋼
の冷延鋼板、低炭素アルミキルド鋼連鋳材をベースとす
るものが用いることができる。また、炭素分が０．００
３ｗｔ％以下の極低炭素鋼やこれにニオブ、チタン等の
金属を添加した非時効性鋼板も使用することができる。BEST MODE FOR CARRYING OUT THE INVENTION The details of the present invention will be described below. [Steel Plates Used] As the steel plates used in the present invention, cold-rolled steel plates of ordinary steel and those based on low carbon aluminized steel continuous cast material can be used. The carbon content is 0.00
Ultra-low carbon steel of 3 wt% or less and non-aging steel sheet in which metals such as niobium and titanium are added can also be used.

【０００６】［Ｓｎめっき］上記の鋼板の少なくとも片
面に形成されるＳｎめっき（下層）において、その形成
に使用されるＳｎめっき浴としては、通常用いられるフ
ェロスタン浴、硫酸浴、塩化浴あるいはフッ化物浴が使
える。めっき量としては、半田性、耐食性を満足するた
めには１ｇ／ｍ２以上あれば良く、上限は特に限定しな
いが、経済的な点から１２ｇ／ｍ２で良い。より好まし
くは４〜１２ｇ／ｍ２の範囲が良い。[Sn Plating] In the Sn plating (lower layer) formed on at least one surface of the above steel sheet, the Sn plating bath used for the formation is a ferrostane bath, a sulfuric acid bath, a chloride bath or a fluoride that is usually used. You can use the bath. The plating amount may be 1 g / m 2 or more in order to satisfy the solderability and the corrosion resistance, and the upper limit is not particularly limited, but 12 g / m 2 is preferable from the economical point of view. The range of 4 to 12 g / m 2 is more preferable.

【０００７】［Ｚｎめっき］本発明において、Ｓｎめっ
き（下層）と上層のＶ層との間に、必要により中間層と
して形成されるＺｎめっきにおいて、その形成に使用さ
れるＺｎめっき浴は通常用いられる硫酸浴、塩化浴が使
える。めっき量としては、熱処理による形成する拡散合
金層が耐食性、耐ホイスカ性を向上させるため、１０ｍ
ｇ／ｍ２以上あれば良く、必要以上に付着量を多くする
と脆いＺｎ−Ｆｅ合金を生成し易くなる傾向があるの
で、上限は１０００ｍｇ／ｍ２で良い。[Zn Plating] In the present invention, in the Zn plating formed as an intermediate layer between the Sn plating (lower layer) and the upper V layer, if necessary, the Zn plating bath used for the formation is usually used. Sulfuric acid bath and chloride bath can be used. The amount of plating is 10 m because the diffusion alloy layer formed by heat treatment improves corrosion resistance and whisker resistance.
The upper limit may be 1000 mg / m 2 , because a g / m 2 or more is sufficient, and if the adhesion amount is increased more than necessary, a brittle Zn-Fe alloy tends to be generated.

【０００８】［Ｖめっき］次に、上層に形成されるＶを
含んだめっき皮膜について述べる。従来から行われてい
る一般的な防錆処理である電解処理による電解クロメー
ト処理皮膜が有害な６価クロムを含む溶液を用いて行わ
れ、さらに電解中に発生するクロム酸ミストが作業環境
に好ましくない影響を与え得るのに対して、Ｖを含んだ
めっきは、６価クロムを含有する処理液を用いずに処理
が可能であり、防錆性も十分有している。耐錆性、半田
性、ホイスカ性、色むらの発生にはＶ付着量が強く影響
しており、Ｖ付着量は５〜４００ｍｇ／ｍ２の範囲とす
る。５ｍｇ／ｍ２未満では、耐錆性の点で問題がある。
４００ｍｇ／ｍ２を超えると 半田性不良、色むらの発
生などで問題がある。また、とくに優れた半田性を要求
する場合には、Ｖ付着量を低く管理した５０ｍｇ／ｍ２
以下が好ましい。ホイスカ性に対しても、Ｖを含んだめ
っきは下層のＳｎあるいはＺｎめっきを施した表面処理
鋼板表面の変質を抑制しており、経時を行った場合のホ
イスカ発生を抑制する効果がある。なお、Ｖは金属とし
てではなく、酸化状態で付着していると考えられる。[V plating] Next, the plating film containing V formed in the upper layer will be described. The electrolytic chromate treatment film by electrolytic treatment, which is a general rust preventive treatment that has been performed conventionally, is performed using a solution containing harmful hexavalent chromium, and chromic acid mist generated during electrolysis is preferable for the working environment. On the other hand, the V-containing plating can be treated without using a treatment liquid containing hexavalent chromium, and has sufficient rust prevention. The V adhesion amount has a strong influence on the rust resistance, solderability, whisker property, and color unevenness, and the V adhesion amount is in the range of 5 to 400 mg / m 2 . If it is less than 5 mg / m 2 , there is a problem in rust resistance.
If it exceeds 400 mg / m 2 , there are problems such as poor solderability and uneven color. When particularly excellent solderability is required, the V adhesion amount is controlled to be low at 50 mg / m 2
The following are preferred. Also for the whisker property, the plating containing V suppresses the deterioration of the surface of the surface-treated steel sheet plated with Sn or Zn of the lower layer, and has the effect of suppressing the generation of whiskers over time. It is considered that V is attached not in the form of metal but in an oxidized state.

【０００９】Ｖを含んだめっき皮膜の付着方法について
は、電解法だけでなく無電解による方法も適用できる。
無電解の方法では、浸漬法、浸漬後ロール絞り法、ロー
ルコート法等が適用できる。Ｖ以外の元素として、Ｍ
ｏ、Ｔｉ、Ｚｒ、Ａｌ、Ｍｇ、Ｐを耐食性向上を目的と
して同時に皮膜中に存在させても良い。処理液として
は、Ｖ化合物に関しては特に制限されるものではないが
一般に入手しやすいフッ化バナジウム、塩化バナジウ
ム、酸化バナジウム、二塩化酸化バナジウム、二臭化酸
化バナジウム、酸化硫酸バナジウムなどのいずれか１種
以上を用いることが好ましい。これらＶ化合物の処理液
中の含有量の総量は３〜１５０ｇ／L、好ましくは５〜
５０ｇ／Lである。３ｇ／L未満の場合は皮膜の生成量が
少なく、良好な皮膜特性が得られない。１５０ｇ／Lを
超えると、皮膜に色むらが発生しやすく、また皮膜の加
工密着性が低下する。さらに薬品が高価であることに加
えて、処理時に鋼板に付着して持ち出される量が増加
し、経済的でなくなる。As a method of depositing a plating film containing V, not only an electrolytic method but also an electroless method can be applied.
As the electroless method, a dipping method, a post-immersion roll drawing method, a roll coating method and the like can be applied. As elements other than V, M
O, Ti, Zr, Al, Mg and P may be simultaneously present in the film for the purpose of improving the corrosion resistance. The treatment liquid is not particularly limited with respect to the V compound, but any one of vanadium fluoride, vanadium chloride, vanadium oxide, vanadium dichloride oxide, vanadium dibromide oxide, vanadium oxide sulfate, etc., which is generally available, is used. It is preferable to use one or more species. The total content of these V compounds in the treatment liquid is 3 to 150 g / L, preferably 5 to
It is 50 g / L. If the amount is less than 3 g / L, the amount of film formed is small and good film characteristics cannot be obtained. If it exceeds 150 g / L, color unevenness is likely to occur in the coating, and the coating adhesion of the coating is reduced. Further, in addition to the expensive chemicals, the amount of the chemicals attached to the steel plate and taken out during processing increases, which is not economical.

【００１０】処理液のｐＨ調整剤として、リン酸、リン
酸塩、ポリリン酸塩、重リン酸塩などのＰ化合物のいず
れか１種以上を用いる。重リン酸塩としては、重リン酸
アンモニウム、重リン酸ナトリウム、重リン酸カルシウ
ム、重リン酸マグネシウム、重リン酸アルミニウムが含
まれる。これらのＰ化合物はｐＨ調整剤として作用する
ばかりでなく、Ｐが処理皮膜中に取り込まれることによ
り、防錆性が向上する。これらＰ化合物をｐＨ調整剤と
して用いる場合の処理液中の含有量は３〜１５０ｇ／
L、好ましくは５〜５０ｇ／Lである。３ｇ／L未満の場
合は皮膜の生成量が少なく、良好な皮膜特性が得られな
い。１５０ｇ／Lを超えると皮膜の加工密着性が低下す
る。さらに処理時に鋼板に付着して持ち出される量が増
加し、経済的でなくなる。As the pH adjuster of the treatment liquid, at least one of P compounds such as phosphoric acid, phosphate, polyphosphate, and heavy phosphate is used. Examples of the heavy phosphate include ammonium heavy phosphate, sodium heavy phosphate, calcium heavy phosphate, magnesium heavy phosphate, and aluminum heavy phosphate. Not only do these P compounds act as pH adjusters, but the incorporation of P into the treated film improves rust prevention. When these P compounds are used as pH adjusters, the content in the treatment liquid is 3 to 150 g /
L, preferably 5 to 50 g / L. If the amount is less than 3 g / L, the amount of film formed is small and good film characteristics cannot be obtained. If it exceeds 150 g / L, the coating adhesion of the coating deteriorates. In addition, the amount of the particles attached to the steel plate during processing increases and is not economical.

【００１１】処理液のｐＨは１〜６、より好ましくは２
〜４の範囲にあることが良い。ｐＨが１未満の場合は皮
膜の析出効率が低下し、十分な厚さの皮膜が得られにく
い。一方、ｐＨが６を超えると処理液が不安定になり、
実用に適さない。また、ＰＨが４を越えて６以下の場合
には、処理液が濁ることがあるが、処理は可能である。
処理液のｐＨはアンモニア水、水酸化ナトリウム、炭酸
ナトリウムなどのアルカリ性物質、または塩酸、硫酸、
硝酸などの酸性物質を添加しても調整可能であるが、皮
膜特性を改善するには、リン酸塩など上記のＰ化合物を
用いることが効果的である。処理浴の温度は２０〜５０
℃の範囲が好ましい。The pH of the treatment liquid is 1 to 6, more preferably 2
It is better to be in the range of ~ 4. If the pH is less than 1, the deposition efficiency of the coating is reduced and it is difficult to obtain a coating having a sufficient thickness. On the other hand, if the pH exceeds 6, the treatment liquid becomes unstable,
Not suitable for practical use. If the pH exceeds 4 and is 6 or less, the treatment liquid may become cloudy, but the treatment is possible.
The pH of the treatment liquid is ammonia water, alkaline substances such as sodium hydroxide and sodium carbonate, or hydrochloric acid, sulfuric acid,
Although it can be adjusted by adding an acidic substance such as nitric acid, it is effective to use the above P compound such as phosphate to improve the film characteristics. The temperature of the treatment bath is 20-50
The range of ° C is preferred.

【００１２】上記の処理液には耐錆性を改善するため
に、さらに水溶性のＭｏ化合物、Ｔｉ化合物、Ｚｒ化合
物、Ａｌ化合物、Ｍｇ化合物を１種以上添加してもよ
い。これらの化合物としては、オキシ硫酸モリブデン、
硫酸チタニル、硫酸ジルコニル、モリブデン酸アンモニ
ウム、チタン酸アンモニウム、硫酸マグネシウム、およ
び前述のＰ化合物である重リン酸マグネシウム、重リン
酸アルミニウムなどが含まれる。処理液中の含有量は、
前記のＶ化合物とこれらのＭｏ化合物、Ｔｉ化合物、Ｚ
ｒ化合物、Ａｌ化合物、またはＭｇ化合物との総量で、
３〜１５０ｇ／L、好ましくは５〜５０ｇ／Lである。３
ｇ／L未満の場合は皮膜の生成量が少なく、良好な皮膜
特性が得られない。１５０ｇ／Lを超えると、皮膜に色
むらが発生しやすく、また皮膜の加工密着性が低下す
る。さらに薬品が高価であることに加えて、処理時に鋼
板に付着して持ち出される量が増加し、経済的でなくな
る。これらの浴中に添加したＭｏ化合物、Ｔｉ化合物、
Ｚｒ化合物、Ａｌ化合物、Ｍｇ化合物に由来する物質
は、Ｖを含んだめっき皮膜中に取り込まれることによ
り、耐錆性が改善する。さらにまた、電導度を向上させ
処理浴を安定させるために、硫酸ナトリウム、硫酸アン
モニウム、塩化アンモニウムなどの塩類を５０ｇ／L以
下含有させても良い。In order to improve rust resistance, one or more water-soluble Mo compounds, Ti compounds, Zr compounds, Al compounds and Mg compounds may be added to the above treatment liquid. These compounds include molybdenum oxysulfate,
Examples include titanyl sulfate, zirconyl sulfate, ammonium molybdate, ammonium titanate, magnesium sulfate, and the above-mentioned P compounds, magnesium diphosphate, aluminum diphosphate, and the like. The content in the processing liquid is
The above V compounds and their Mo compounds, Ti compounds, Z
r compound, Al compound, or Mg compound,
It is 3 to 150 g / L, preferably 5 to 50 g / L. Three
If it is less than g / L, the amount of film formed is small and good film characteristics cannot be obtained. If it exceeds 150 g / L, color unevenness is likely to occur in the coating, and the coating adhesion of the coating is reduced. Further, in addition to the expensive chemicals, the amount of the chemicals attached to the steel plate and taken out during processing increases, which is not economical. Mo compounds, Ti compounds added to these baths,
A substance derived from a Zr compound, an Al compound, and a Mg compound is incorporated into the plating film containing V, so that the rust resistance is improved. Furthermore, in order to improve the conductivity and stabilize the treatment bath, salts such as sodium sulfate, ammonium sulfate and ammonium chloride may be contained in an amount of 50 g / L or less.

【００１３】上記のようにして作成した処理浴を用い、
鋼板に処理皮膜を生成させる。処理方法としては浸漬処
理、陰極電解処理のいずれも可能である。浸漬処理の場
合、１〜６０秒、好ましくは２〜１０秒で十分な厚さの
処理皮膜が得られる。６０秒以上浸漬しても皮膜の厚さ
はそれ程増加しなくなる。電解処理の場合は短時間で厚
い皮膜が得られ、０.５〜１００Ａ／ｄｍ２が好まし
い。０.５Ａ／ｄｍ２未満では皮膜の成長に時間がかか
り過ぎ、短時間で厚い皮膜を得ることができない。電流
密度は処理液のｐＨの影響を受けるが、酸性領域では高
ｐＨ側のｐＨ６の場合、１００Ａ／ｄｍ２を超えるとヤ
ケを生じ、均一な皮膜が得られない。また処理皮膜が厚
くなると、加工密着性が低下する。Using the treatment bath prepared as described above,
Generate a treatment film on the steel plate. As the treatment method, either dipping treatment or cathodic electrolysis treatment is possible. In the case of the dipping treatment, a treatment film having a sufficient thickness can be obtained in 1 to 60 seconds, preferably 2 to 10 seconds. Even if it is immersed for 60 seconds or more, the thickness of the film does not increase so much. In the case of electrolytic treatment, a thick film can be obtained in a short time, and 0.5-100 A / dm 2 is preferable. If it is less than 0.5 A / dm 2 , it takes too much time for the film to grow, and a thick film cannot be obtained in a short time. Although the current density is affected by the pH of the treatment liquid, in the case of pH 6 on the high pH side in the acidic region, when it exceeds 100 A / dm 2 , burns occur and a uniform film cannot be obtained. Further, as the treated film becomes thicker, the work adhesion decreases.

【００１４】［熱処理による拡散合金層］本発明におい
ては、上述したＶを含んだめっき皮膜の形成に先だっ
て、或いはＶを含んだめっき皮膜を形成した後に、熱処
理を施すことができる。この場合、中間層としてＺｎめ
っきを形成する時には、Ｚｎめっきを形成した後に熱処
理を施すのがよい。かかる熱処理は板温が１５０〜４０
０℃の範囲がよい。１５０℃未満では、拡散速度が遅く
なり、工業的に不経済である。熱処理によりＳｎ−Ｆｅ
合金が形成するとともに、Ｓｎの融点以上の温度で熱処
理を施した場合には、Ｓｎ溶融によりめっき表層は平滑
度が向上し、光沢のある美麗な外観が得られる。また、
４００℃を越える場合にはＳｎ溶融およびＳｎ−Ｆｅ合
金形成が過度になり過ぎるとともに、特にＺｎめっきを
施した場合には、脆いＺｎ−Ｆｅ合金が形成しやすくな
るので好ましくない。加熱時間は温度に依存し、温度が
低い場合は比較的長い処理時間が必要であり、温度が高
い場合には短時間処理が可能である。時間は生産性を考
慮すると０.２〜１２０秒間の処理が好ましい。この熱
処理は、めっき皮膜中の残留応力を低減し、ホイスカの
発生を抑制するので、特に厳しく耐ホイスカ性を要求さ
れる場合には実施する方が好ましい。加熱方法について
はガスおよび電気を使用するのが一般的であり、通電抵
抗加熱、高周波誘導加熱あるいはこれらの組み合わせが
可能である。雰囲気としては大気中で良いが、非酸化性
の雰囲気を使用した方がめっき表面の酸化が抑制出来る
のでより好ましい。なお、Ｖを含んだめっきを施した後
に熱処理を施した場合には、最表層のＶが下層に拡散す
るため、ホイスカ性には効果があるが、熱処理を施さず
に最表層にＶを含んだめっきを施したままの鋼板に比較
すると、やや耐食性向上効果が低下する傾向が認められ
る。[Diffusion Alloy Layer by Heat Treatment] In the present invention, heat treatment can be performed prior to the formation of the above V-containing plating film or after the formation of the V-containing plating film. In this case, when Zn plating is formed as the intermediate layer, it is preferable to perform heat treatment after forming Zn plating. Such heat treatment has a plate temperature of 150 to 40
A range of 0 ° C is preferable. If it is less than 150 ° C, the diffusion rate becomes slow, which is industrially uneconomical. Sn-Fe by heat treatment
When an alloy is formed and heat treatment is performed at a temperature equal to or higher than the melting point of Sn, the Sn melting improves the smoothness of the plating surface layer, and a glossy and beautiful appearance is obtained. Also,
If the temperature exceeds 400 ° C., Sn melting and Sn—Fe alloy formation become excessive, and especially when Zn plating is performed, a brittle Zn—Fe alloy is likely to be formed, which is not preferable. The heating time depends on the temperature. When the temperature is low, a relatively long treatment time is required, and when the temperature is high, a short treatment time is possible. The processing time is preferably 0.2 to 120 seconds in consideration of productivity. This heat treatment reduces residual stress in the plating film and suppresses the generation of whiskers. Therefore, it is preferable to perform this heat treatment particularly when whisker resistance is required. As a heating method, gas and electricity are generally used, and energization resistance heating, high frequency induction heating, or a combination thereof is possible. The atmosphere may be air, but it is more preferable to use a non-oxidizing atmosphere because oxidation of the plating surface can be suppressed. In addition, when heat treatment is performed after plating containing V, V in the outermost layer diffuses to the lower layer, which is effective for whiskerability, but V is included in the outermost layer without heat treatment. It can be seen that the effect of improving the corrosion resistance is slightly lower than that of the steel sheet that has been subjected to the edging.

【００１５】[0015]

【実施例】以下に、本発明を実施例に基づいてさらに説
明する。 ［実施例１〜２０］厚さ０.６ｍｍの冷延鋼板を通常の
方法で脱脂、酸洗の前処理を行った。次に下記の条件で
Ｓｎめっき、Ｚｎめっきを行った。EXAMPLES The present invention will be further described below based on examples. [Examples 1 to 20] A cold-rolled steel sheet having a thickness of 0.6 mm was subjected to degreasing and pickling pretreatments by a usual method. Next, Sn plating and Zn plating were performed under the following conditions.

【００１６】［Ｓｎめっきの条件］ ［浴組成］ 硫酸錫 ８０ｇ／Ｌ フェノールスルフォン酸 ６０ｇ／Ｌ ノイゲンＥＮ ５ｇ／Ｌ ［めっき条件］ 浴温度 ５０±２℃ 電流密度 ５〜３０Ａ／ｄｍ２ 電解時間 ２〜２０秒[Sn plating conditions] [Bath composition] Tin sulfate 80 g / L Phenolsulfonic acid 60 g / L Neugen EN 5 g / L [Plating conditions] Bath temperature 50 ± 2 ° C. Current density 5-30 A / dm 2 Electrolysis time 2 ~ 20 seconds

【００１７】［Ｚｎめっきの条件］ ［浴組成］ 硫酸亜鉛 ２５０ｇ／Ｌ 硫酸アンモニウム ３０ｇ／Ｌ ［めっき条件］ 浴温度 ４０±２℃ 電流密度 ５〜３０Ａ／ｄｍ２ 電解時間 ０.１〜５秒[Zn plating conditions] [Bath composition] Zinc sulfate 250 g / L Ammonium sulfate 30 g / L [Plating conditions] Bath temperature 40 ± 2 ° C. Current density 5-30 A / dm 2 Electrolysis time 0.1-5 seconds

【００１８】Ｓｎめっき量を変化させてＳｎめっき、あ
るいは、Ｓｎめっき後に引き続いてＺｎめっき量を変化
させてＺｎめっきを行い、乾燥を行った。一部の試料に
ついては、乾燥後に２８５±１５℃で０.５秒熱処理に
よる拡散処理を行った。引き続いて、全ての実施例につ
いてＶを含んだめっきを施した。さらに、一部の試料に
ついては、Ｖを含んだめっき後に２８５±１５℃で０.
５秒熱処理による拡散処理を行った。Sn plating was performed by changing the Sn plating amount, or Zn plating was performed by changing the Zn plating amount after the Sn plating and then drying. After drying, some samples were subjected to diffusion treatment by heat treatment at 285 ± 15 ° C. for 0.5 seconds. Subsequently, plating containing V was applied to all the examples. Furthermore, for some of the samples, after plating containing V, at 285 ± 15 ° C.
Diffusion treatment was performed by heat treatment for 5 seconds.

【００１９】Ｖを含んだめっきの条件を表１と２に示
す。一部の処理液には水溶性のＭｏ化合物、Ｔｉ化合
物、Ｚｒ化合物、Ａｌ化合物、Ｍｇ化合物を１種以上を
添加した。処理液のＰＨ調整としてＰ化合物を使用し
た。Ｐ化合物だけでは目的とするＰＨにならない場合
は、微調整にアンモニア水、水酸化ナトリウム、炭酸ナ
トリウムなどのアルカリ性物質、または塩酸、硫酸、硝
酸などの酸性物質を添加した。The plating conditions including V are shown in Tables 1 and 2. One or more water-soluble Mo compounds, Ti compounds, Zr compounds, Al compounds, and Mg compounds were added to some of the treatment liquids. The P compound was used for adjusting the pH of the treatment liquid. When the desired PH was not achieved with only the P compound, an alkaline substance such as aqueous ammonia, sodium hydroxide or sodium carbonate, or an acidic substance such as hydrochloric acid, sulfuric acid or nitric acid was added for fine adjustment.

【００２０】［比較例１〜２］比較例として、市販のぶ
りき（Ｓｎめっき量：５．６ｇ／ｍ２と１１．２ｇ／ｍ
２）の２種類を用いた。いずれの比較例もリフロー処理
を行ったサンプルである。[Comparative Examples 1 and 2] As comparative examples, commercially available tinplate (Sn plating amount: 5.6 g / m 2 and 11.2 g / m).
2 ) were used. Each of the comparative examples is a sample subjected to reflow processing.

【００２１】実施例及び比較例における表面処理鋼板の
特性は以下のようにして測定した。 （１）半田性 サンプルを幅１０ｍｍ、長さ５０ｍｍに切り出し、レス
カ製のソルダーチェッカー（型式：ＳＡＴ５０００）を
用いてゼロクロスタイムを測定した。半田濡れ性に優れ
るものほど、ゼロクロスタイムは短くなる。半田として
ＪＩＳ Ｚ３２８２の６０Ｐｂ−４０Ｓｎ％のＨ６０Ａ
（タルチン製）を、フラックスとしてＮＡ２００（タム
ラ化研製）を用いて行った。The characteristics of the surface-treated steel sheets in Examples and Comparative Examples were measured as follows. (1) A solderability sample was cut into a width of 10 mm and a length of 50 mm, and zero cross time was measured using a solder checker (model: SAT5000) manufactured by Lesca. The higher the solder wettability, the shorter the zero cross time. JIS Z3282 60Pb-40Sn% H60A as solder
(Tartin) was used as a flux using NA200 (Tamura Kaken).

【００２２】（２）耐錆性 ＪＩＳ−Ｚ２３７１に基づいた塩水噴霧試験を１２時間
実施した後、表面を目視観察し、次に示す５段階の評点
で評価した。評点４と５を合格とした。 評点５：表面に変化が認められない。 評点４：０％＜表面全体の点状錆≦１０％ 評点３：１０％＜表面全体の点状錆≦４９％ 評点２：４９％＜表面全体の点状錆≦７５％ 評点１：表面全体の点状錆＞７５％(2) Rust resistance After a salt spray test based on JIS-Z2371 was carried out for 12 hours, the surface was visually observed and evaluated by the following 5 grades. Scores 4 and 5 were passed. Rating 5: No change is observed on the surface. Score 4: 0% <Spotted rust on the entire surface ≤ 10% Score 3: 10% <Spotted rust on the entire surface ≤ 49% Score 2: 49% <Spotted rust on the entire surface ≤ 75% Score 1: Whole surface Point rust> 75%

【００２３】（３）導電性 低抵抗率計（三菱化学製、型式：ロレスターＧＰ ＭＣ
Ｐ−Ｔ６００）を用いて、ＪＩＳＫ７１９４に準じた四
探針接触抵抗を測った。０.１ｍΩ未満を（○）、０.１
ｍΩ以上を（×）で表示した。評価○を合格とした。(3) Conductive low resistivity meter (manufactured by Mitsubishi Chemical, model: Lorester GP MC
P-T600) was used to measure the contact resistance of the four-point probe according to JIS K7194. Less than 0.1 mΩ (○), 0.1
MΩ or more is indicated by (x). The evaluation ◯ was passed.

【００２４】（４）耐ホイスカ性 ９０°折曲げ加工した板（片側面積：３０×３０ｍ
ｍ２）あるいは深絞り加工（内径３０ｍｍ）したカップ
を恒温恒湿雰囲気（６０℃、９５％ＲＨ）で６０日経時
させた。経時後、９０°折曲げ加工部の内側及び絞り比
２で深絞り加工（内径３０ｍｍ）したカップの内面を走
査型顕微鏡で観察し、長さ１０μｍ以上のらせん状ある
いは針状のホイスカ発生の有無で評価した。(4) Whisker resistance 90 ° bent plate (one side area: 30 × 30 m)
m 2 ) or the deep-drawn cup (inner diameter 30 mm) was aged for 60 days in a constant temperature and constant humidity atmosphere (60 ° C., 95% RH). After the passage of time, the inside of the 90 ° bent portion and the inner surface of the cup deep-drawn (inner diameter 30 mm) with a drawing ratio of 2 were observed with a scanning microscope, and the presence of spiral or needle whiskers with a length of 10 μm or more. It was evaluated by.

【００２５】表３にＳｎめっき量、Ｚｎめっき量、Ｖを
含んだめっき皮膜中のＶ量、熱処理の有無および特性を
示すように、実施例１〜２０は比較例に比べて、半田性
と導電性はほぼ同レベルであった。実施例１〜２０の耐
錆性は、比較例に比べて良好であった。比較例１と２で
は、ホイスカの発生が認められたが、熱処理による拡散
処理を行った実施例１〜２０では、長さ１０μｍ以上の
らせん状あるいは針状のホイスカの発生は認められなか
った。As Table 3 shows the Sn plating amount, the Zn plating amount, the V amount in the plating film containing V, the presence / absence of heat treatment and the characteristics, Examples 1 to 20 are different from each other in solderability and The conductivity was almost at the same level. The rust resistance of Examples 1 to 20 was better than that of Comparative Example. Whiskers were found to be generated in Comparative Examples 1 and 2, but spiral or needle-shaped whiskers having a length of 10 μm or more were not found in Examples 1 to 20 in which diffusion treatment by heat treatment was performed.

【００２６】[0026]

【表１】 [Table 1]

【００２７】[0027]

【表２】 [Table 2]

【００２８】[0028]

【表３】 [Table 3]

【００２９】[0029]

【発明の効果】以上のように本発明の表面処理鋼板は、
下層としてＳｎめっき、上層としてＶを含んだ層を存在
させたものである。さらに、中間層としてＺｎめっきを
行っても良く、半田性、耐錆性及び導電性に優れてい
る。これらの表面処理鋼板は熱処理を行っても良く、熱
処理により耐ホイスカ性に優れる。As described above, the surface-treated steel sheet of the present invention is
The lower layer is Sn plating, and the upper layer is a layer containing V. Furthermore, Zn plating may be performed as the intermediate layer, and the solderability, rust resistance and conductivity are excellent. These surface-treated steel sheets may be heat-treated, and are excellent in whisker resistance.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 駒井 正雄 山口県下松市東豊井1296番地の１ 東洋鋼 鈑株式会社技術研究所内 Ｆターム(参考） 4K024 AA01 AA05 AA07 AB02 AB03 BA03 BB09 BC01 DB01 DB03 GA04 GA14 GA16 4K026 AA02 AA07 AA10 AA12 AA22 BA08 BB08 BB10 CA13 CA18 CA25 CA30 CA33 EB11 4K044 AA02 AB02 BA10 BA12 BB03 BB04 BC02 BC08 BC14 CA16 CA18 CA53 CA62    ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masao Komai             1 Toyo Steel at 1296 Higashitoyoi, Kudamatsu City, Yamaguchi Prefecture             Inside the Technology Research Center F-term (reference) 4K024 AA01 AA05 AA07 AB02 AB03                       BA03 BB09 BC01 DB01 DB03                       GA04 GA14 GA16                 4K026 AA02 AA07 AA10 AA12 AA22                       BA08 BB08 BB10 CA13 CA18                       CA25 CA30 CA33 EB11                 4K044 AA02 AB02 BA10 BA12 BB03                       BB04 BC02 BC08 BC14 CA16                       CA18 CA53 CA62

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 鋼板の少なくとも片面に、下層としてＳ
ｎめっき４〜１２ｇ／ｍ２、上層にＶ量が５〜４００ｍ
ｇ／ｍ２の層を有していることを特徴とする電子部品用
表面処理鋼板。1. An S-layer as a lower layer on at least one surface of a steel sheet.
n plating 4 to 12 g / m 2 , V amount of 5 to 400 m in upper layer
A surface-treated steel sheet for electronic parts, having a layer of g / m 2 . 【請求項２】 前記下層と上層との間に、中間層として
Ｚｎめっき１０〜１０００ｍｇ／ｍ２の層が形成されて
いる請求項１に記載の電子部品用表面処理鋼板。 2. The surface-treated steel sheet for electronic parts according to claim 1, wherein a layer of Zn plating of 10 to 1000 mg / m 2 is formed as an intermediate layer between the lower layer and the upper layer. 【請求項３】 鋼板の少なくとも片面に、下層としてＳ
ｎめっき４〜１２ｇ／ｍ２の層を形成し、更に上層とし
てＶ量が５〜４００ｍｇ／ｍ２の層を形成する電子部品
用表面処理鋼板の製造方法において、前記Ｓｎめっき層
（下層）を形成した後前記Ｖ層（上層）の形成に先だっ
て、又は前記Ｖ層（上層）を形成した後に、熱処理を施
すことを特徴とする製造方法。3. A steel sheet having at least one surface on which S is formed as a lower layer.
In the method for producing a surface-treated steel sheet for electronic parts, which comprises forming a layer of n plating 4 to 12 g / m 2 and further forming a layer having a V amount of 5 to 400 mg / m 2 as an upper layer, the Sn plating layer (lower layer) is added. After the formation, prior to forming the V layer (upper layer), or after forming the V layer (upper layer), heat treatment is performed. 【請求項４】 前記熱処理を、板温を１５０〜４００℃
の範囲として行なう請求項３に記載の製造方法。4. The plate temperature of the heat treatment is 150 to 400 ° C.
The manufacturing method according to claim 3, wherein the manufacturing method is performed as follows. 【請求項５】 鋼板の少なくとも片面に、下層としてＳ
ｎめっき４〜１２ｇ／ｍ２を形成し、次いで中間層とし
てＺｎめっき１０〜１０００ｍｇ／ｍ２を形成し、更に
上層としてＶ量が５〜４００ｍｇ／ｍ２の層を形成する
電子部品用表面処理鋼板の製造方法において、前記Ｚｎ
めっき層（中間層）を形成した後前記Ｖ層（上層）の形
成に先だって、又は前記Ｖ層（上層）を形成した後に、
熱処理を施すことを特徴とする製造方法。5. A steel sheet having at least one surface on which S is formed as a lower layer.
an n plating 4~12g / m 2, then the Zn plating 10 to 1000 mg / m 2 was formed as an intermediate layer, further electronic components for surface treatment amount of V to form a layer of 5 to 400 mg / m 2 as an upper layer In the method for producing a steel sheet, the Zn
After forming the plating layer (intermediate layer) and before forming the V layer (upper layer), or after forming the V layer (upper layer),
A manufacturing method characterized by performing heat treatment. 【請求項６】 前記熱処理は、板温を１５０〜４００℃
の範囲として行なう請求項５に記載の製造方法。6. The plate temperature of the heat treatment is 150 to 400 ° C.
The manufacturing method according to claim 5, wherein the manufacturing method is performed as follows.
JP2001298098A 2001-09-27 2001-09-27 Surface-treated steel sheet for electronic parts and manufacturing method thereof Expired - Fee Related JP4954406B2 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005002368A (en) * 2003-06-09 2005-01-06 Ishihara Chem Co Ltd Tin plating bath for preventing whisker
JP2005097669A (en) * 2003-09-24 2005-04-14 Ishihara Chem Co Ltd Liquid and method for post-treating plated surface
JP2016084527A (en) * 2014-10-24 2016-05-19 Ｊｆｅスチール株式会社 Steel sheet for vessel and manufacturing method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5192739A (en) * 1975-02-13 1976-08-14 Tairyukaseito taisumatsujiseino suguretadenkiburiki
JPS63277786A (en) * 1986-12-05 1988-11-15 Toyo Kohan Co Ltd Two-ply plated steel sheet for soldering
JPH03291386A (en) * 1990-04-09 1991-12-20 Nippon Steel Corp Surface treated steel sheet for electronic equipment parts
JP2001073185A (en) * 1999-09-07 2001-03-21 Toyo Kohan Co Ltd Surface treated steel sheet and its production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5192739A (en) * 1975-02-13 1976-08-14 Tairyukaseito taisumatsujiseino suguretadenkiburiki
JPS63277786A (en) * 1986-12-05 1988-11-15 Toyo Kohan Co Ltd Two-ply plated steel sheet for soldering
JPH03291386A (en) * 1990-04-09 1991-12-20 Nippon Steel Corp Surface treated steel sheet for electronic equipment parts
JP2001073185A (en) * 1999-09-07 2001-03-21 Toyo Kohan Co Ltd Surface treated steel sheet and its production

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005002368A (en) * 2003-06-09 2005-01-06 Ishihara Chem Co Ltd Tin plating bath for preventing whisker
JP2005097669A (en) * 2003-09-24 2005-04-14 Ishihara Chem Co Ltd Liquid and method for post-treating plated surface
JP2016084527A (en) * 2014-10-24 2016-05-19 Ｊｆｅスチール株式会社 Steel sheet for vessel and manufacturing method thereof

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