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JP2797983B2 - Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties - Google Patents

Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties

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Publication number
JP2797983B2
JP2797983B2 JP6258357A JP25835794A JP2797983B2 JP 2797983 B2 JP2797983 B2 JP 2797983B2 JP 6258357 A JP6258357 A JP 6258357A JP 25835794 A JP25835794 A JP 25835794A JP 2797983 B2 JP2797983 B2 JP 2797983B2
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JP
Japan
Prior art keywords
steel sheet
corrosion resistance
coated steel
film
composite coated
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
Application number
JP6258357A
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Japanese (ja)
Other versions
JPH08120461A (en
Inventor
和義 田村
弘行 長井
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.)
Nippon Steel Corp
Original Assignee
Sumitomo Metal Industries 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 Sumitomo Metal Industries Ltd filed Critical Sumitomo Metal Industries Ltd
Priority to JP6258357A priority Critical patent/JP2797983B2/en
Publication of JPH08120461A publication Critical patent/JPH08120461A/en
Application granted granted Critical
Publication of JP2797983B2 publication Critical patent/JP2797983B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26After-treatment
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C28/00Coating 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
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38Chromatising

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、自動車、家電製品、建
材等の材料として好適な、耐食性および電着塗装性に優
れた有機複合被覆鋼板に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic composite coated steel sheet excellent in corrosion resistance and electrodeposition paintability, which is suitable as a material for automobiles, home electric appliances, building materials and the like.

【0002】[0002]

【従来の技術】近年、自動車用をはじめとして、多くの
産業分野で各種の表面処理金属板 (主として鋼板) が使
用されている。使用量の増加に伴い、性能への要求も高
まる一方であり、特に自動車用においては、「耐孔あき
10年保証」というような長期的な高耐食性が求められて
いる。
2. Description of the Related Art In recent years, various surface-treated metal sheets (mainly, steel sheets) have been used in many industrial fields including automobiles. The demand for performance is increasing with the increase in usage, and especially for automobiles,
Long-term high corrosion resistance such as "10-year warranty" is required.

【0003】従来より自動車車体用の防錆鋼板として、
数々の表面処理鋼板が発明され、実用化されてきた。そ
の中でも、亜鉛または亜鉛系合金めっき鋼板の上に、ク
ロメート皮膜層と薄い樹脂皮膜層を有する、いわゆる有
機複合被覆鋼板は、クロメート皮膜の防食作用、有機被
覆の腐食環境遮断効果などの作用により、種々の防錆鋼
板の中でも、圧倒的に優れた耐食性を有している。しか
し、近年自動車メーカの耐食性向上ニーズはより一層高
度化し、より耐食性能の優れた表面処理鋼板が要求され
ている。
Conventionally, as a rust-preventive steel plate for an automobile body,
Numerous surface-treated steel sheets have been invented and put into practical use. Among them, a so-called organic composite coated steel sheet having a chromate film layer and a thin resin film layer on a zinc or zinc-based alloy-plated steel sheet, the anti-corrosion effect of the chromate film, the effect of blocking the corrosion environment of the organic coating, etc. Among various rust-proof steel plates, it has overwhelmingly excellent corrosion resistance. However, in recent years, the needs of automobile manufacturers for improving corrosion resistance have been further enhanced, and surface-treated steel sheets having more excellent corrosion resistance have been demanded.

【0004】これまで、例えば特開平2−145774号公報
には、母材たるめっき鋼板の表面粗度RMAX を有機樹脂
皮膜の12倍以上で、かつPPI を30以上と、鋼板の表面粗
度を規定した有機複合被覆鋼板が、また、特開平2−27
0546号公報には、表面粗度Rz を有機樹脂皮膜厚の1.0
〜5.0 倍とした有機複合被覆鋼板が報告されている。い
ずれも、表面粗度を有機樹脂皮膜厚より大きくすること
で、有機樹脂皮膜を施す際、局所的に皮膜の薄い部分を
作り、スポット溶接性を確保しようとするものである。
しかしながら、両技術では凸部でクロメート皮膜や有機
樹脂皮膜が薄いかまたは形成されない状態となる。その
結果、凸部で腐食が進行し易く、耐食性を低下させる問
題を生じる。
Until now, for example, Japanese Patent Application Laid-Open No. 2-145774 discloses that the surface roughness R MAX of a plated steel sheet as a base material is 12 times or more that of an organic resin film and the PPI is 30 or more, The organic composite coated steel sheet which defines
Japanese Patent No. 0546 discloses that the surface roughness Rz is set to a value of 1.0 for the thickness of the organic resin film.
Organic composite coated steel sheets with a ratio of up to 5.0 times have been reported. In any case, when the surface roughness is made larger than the thickness of the organic resin film, a thin portion of the film is locally formed when the organic resin film is applied, so as to secure spot weldability.
However, in both techniques, the chromate film or the organic resin film is thin or not formed at the convex portion. As a result, corrosion tends to progress at the convex portions, and there is a problem that the corrosion resistance is reduced.

【0005】さらにクロメートを塗布する際、鋼板表面
の凹部にクロメート液が溜まり、焼き付け後のクロメー
ト付着量が微視的に不均一になる。クロメート付着量と
電着塗装膜厚の間には相関があり、5mm2 当たり0.1 μ
g以下の付着量では、電着塗装膜厚が厚くなる傾向があ
る。そのため、クロメート付着量が微視的に不均一であ
れば、電着塗装後に塗装むらを発生させる。
Further, when the chromate is applied, the chromate liquid accumulates in the concave portions on the surface of the steel sheet, and the amount of the attached chromate after baking becomes microscopically nonuniform. There is a correlation between the amount of chromate coating and the thickness of the electrodeposition coating, 0.1 μm per 5 mm 2
When the amount is less than g, the electrodeposition coating film thickness tends to be large. For this reason, if the chromate adhesion amount is microscopically nonuniform, uneven coating occurs after the electrodeposition coating.

【0006】そのため、クロメート付着量を増したり有
機樹脂皮膜を厚くする方法が考えられるが、経済的でな
く、また溶接時の鋼板表面の電気抵抗が高くなりすぎ、
電極表面へのカーボン汚れが増大するなどの理由によ
り、溶接性を著しく低下させるなどの問題を生じる。
For this reason, a method of increasing the amount of chromate adhering or increasing the thickness of the organic resin film can be considered, but it is not economical and the electric resistance of the steel sheet surface during welding becomes too high.
For example, carbon contamination on the electrode surface is increased, which causes a problem such as a remarkable decrease in weldability.

【0007】その他、特開平4−381 号公報では合金化
溶融亜鉛めっき鋼板に限定してRzを1.2 μm以下にす
ることで、良好な耐食性が得られるとの報告がある。し
かし、クロメートに関する規定がなされていない。
In addition, Japanese Patent Application Laid-Open No. 4-381 reports that good corrosion resistance can be obtained by limiting Rz to 1.2 μm or less only for galvannealed steel sheets. However, there is no provision regarding chromate.

【0008】また、クロメートの微視的な付着量分布に
ついて記載したものとして特開平6−57447 号公報 (特
願平4−212505号) および特開平6−116778号公報( 特
願平4−264833号) があり、どちらもEPMAの点分析でCr
の特性X線強度の平均値Xとその標準偏差σとの比が、
σ/X≦0.3 とした有機複合被覆鋼板について報告して
いる。この場合、クロメートは鋼板上に均一に分散して
おり、その結果、優れた溶接性および耐チッピング性が
得られると報告している。しかし、これらには表面粗度
に関する記載がなされていない。
Japanese Patent Application Laid-Open Nos. Hei 6-57447 (Japanese Patent Application No. 4-212505) and Japanese Unexamined Patent Publication No. Hei 6-116778 (Japanese Patent Application No. 4-264833) describe the microscopic adhesion amount distribution of chromate. No.), both of which were Cr in EPMA point analysis
The ratio between the average value X of the characteristic X-ray intensities and its standard deviation σ is
It reports on an organic composite coated steel sheet with σ / X ≦ 0.3. In this case, it is reported that the chromate is uniformly dispersed on the steel sheet, resulting in excellent weldability and chipping resistance. However, these documents do not describe the surface roughness.

【0009】[0009]

【発明が解決しようとする課題】本発明では上記問題点
を解決し、耐食性および電着塗装性に優れた有機複合被
覆鋼板を提供することを目的とする。具体的には本発明
の目的は、自動車内外装用材料に耐えうる耐食性および
電着性 (評点合計≧16点) を備えた有機複合被覆鋼板を
提供することである。
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide an organic composite coated steel sheet having excellent corrosion resistance and electrodeposition coating properties. Specifically, an object of the present invention is to provide an organic composite coated steel sheet having corrosion resistance and electrodeposition properties (total score ≧ 16 points) that can withstand materials for automobile interior and exterior.

【0010】[0010]

【課題を解決するための手段】上記の事情に鑑み、本発
明者らは有機複合被覆鋼板の耐食性および電着塗装性を
向上させる方法を鋭意検討した結果、有機複合被覆鋼板
に使用する亜鉛めっきもしくは亜鉛系合金めっきの表面
粗度Rz(十点平均粗さ) とRa(中心線平均粗さ) がRa
≦0.13×Rz なる関係を満たし、かつPPI が30以上であ
り、さらにそのような鋼板上の任意の部分において、そ
の上層にCr付着量として、5mm2 当たり、0.1 μg以上
のクロメート皮膜を有する有機複合被覆鋼板が有効であ
るという知見を得て、本発明に至ったのである。
In view of the above circumstances, the present inventors have intensively studied a method for improving the corrosion resistance and the electrodeposition coating property of an organic composite coated steel sheet. Alternatively, the surface roughness Rz (ten-point average roughness) and Ra (center line average roughness) of the zinc-based alloy plating are Ra.
≤ 0.13 × Rz, and PPI is 30 or more, and in any part on such a steel sheet, an organic layer having a chromate film of 0.1 μg or more per 5 mm 2 as a Cr adhesion amount on an upper layer thereof. The knowledge that the composite coated steel sheet is effective led to the present invention.

【0011】ここに、本発明の要旨とするところは、亜
鉛めっきもしくは亜鉛系合金めっき鋼板の少なくとも片
面上に、第1層として鋼板上の任意の5mm2 に、Cr付着
量として0.1 μg以上のクロメート皮膜を有し、その上
層に第2層として0.1 μm以上の有機樹脂皮膜を有する
有機複合被覆鋼板であって、母材たる前記めっき鋼板の
中心線平均粗さRa と十点平均粗さRz がRa ≦0.13×
z なる関係を満たし、かつ、該めっき鋼板の下記表面
粗度パラメータPPIが30以上であることを特徴とする
耐食性および電着塗装性に優れた有機複合被覆鋼板であ
る。PPI:1インチ当たりの山の数。但し、しきい値
をRMAX の30%以上とする。
Here, the gist of the present invention is that at least one side of a galvanized or zinc-based alloy-plated steel sheet has a first layer of an arbitrary 5 mm 2 on the steel sheet and a Cr adhesion amount of 0.1 μg or more. An organic composite coated steel sheet having a chromate film and an organic resin film having a thickness of 0.1 μm or more as a second layer thereon, wherein a center line average roughness Ra and a ten-point average roughness R of the plated steel plate as a base material are provided. z is Ra ≦ 0.13 ×
An organic composite coated steel sheet excellent in corrosion resistance and electrodeposition coating property, which satisfies a relationship of R z and has a surface roughness parameter PPI of 30 or more of the plated steel sheet. PPI: number of peaks per inch. However, the the 30% or more of R MAX threshold.

【0012】[0012]

【作用】以下、本発明の構成と作用について詳述する。
本発明は、従来の有機複合被覆鋼板の母材のめっき鋼板
として、Rz(十点平均粗さ) とRa(中心線平均粗さ) が
Ra ≦0.13×Rz なる関係を満たし、かつPPIが30以上
である鋼板を使用し、その上に第1層として鋼板上の任
意の5mm2 を測定し、Cr付着量として0.1 μg以上のク
ロメート皮膜を有する点に特徴がある。したがって、母
材のめっき鋼板の種類やめっき付着量、第1層クロメー
ト皮膜、第2層有機樹脂皮膜などについては、従来の有
機複合被覆鋼板と同様でよく、特に制限されないが、こ
れらについても次に簡単に説明する。
The structure and operation of the present invention will be described below.
According to the present invention, as a conventional plated steel sheet of a base material of an organic composite coated steel sheet, Rz (ten-point average roughness) and Ra (center line average roughness) satisfy a relationship of Ra ≦ 0.13 × Rz, and a PPI of 30. The steel sheet described above is used, and an arbitrary 5 mm 2 on the steel sheet is measured as a first layer on the steel sheet, and a feature is that a chromate film having a Cr adhesion amount of 0.1 μg or more is provided. Therefore, the type of the base steel sheet, the coating weight, the first layer chromate film, the second layer organic resin film and the like may be the same as those of the conventional organic composite coated steel sheet, and are not particularly limited. A brief description is given below.

【0013】母材めっき鋼板 本発明に用いられるめっき鋼板は亜鉛もしくは亜鉛系合
金めっき鋼板で、その製法は電気めっき、溶融めっき等
の常法により、特に制限されず、片面めっきおよび両面
めっきのいずれでもよい。めっき付着量は特に制限され
ないが、加工性と耐食性のバランスから片面当たり10〜
60g/m2の範囲内が好ましい。本発明において、鋼板はR
a ≦0.13×Rz を満たし、かつPPI が30以上のものを用
いる。
Base- coated steel sheet The coated steel sheet used in the present invention is a zinc- or zinc-based alloy-coated steel sheet, and its production method is not particularly limited by a conventional method such as electroplating and hot-dip plating. May be. The amount of plating is not particularly limited, but is 10 to 10 per side from the balance between workability and corrosion resistance.
It is preferably in the range of 60 g / m 2 . In the present invention, the steel sheet is R
Use a material that satisfies a ≦ 0.13 × Rz and has a PPI of 30 or more.

【0014】ここで、Ra ≦0.13×Rz は鋼板表面粗度
の上限を規定しており、一方、PPIが30以上ということ
は、鋼板表面凹凸の数が30%以上であることを意味す
る。ただし、「しきい値をRMAX の30%以上とする」と
は、Max の30%以上の凸部を1山として数えることを意
味する。
Here, Ra ≦ 0.13 × Rz specifies the upper limit of the surface roughness of the steel sheet. On the other hand, when the PPI is 30 or more, it means that the number of irregularities on the surface of the steel sheet is 30% or more. However, "the threshold to 30% or more of R MAX" is meant that the count of 30% or more of the projections of Max as a mountain.

【0015】したがって、本発明において母材鋼板の表
面性状を上述のように規定することの作用効果上の意義
は次の通りである。上述の範囲内の表面凹凸を有する鋼
板を使用すれば、クロメート層および有機樹脂皮膜層を
均一に塗布できることを意味する。
Therefore, in the present invention, defining the surface properties of the base steel sheet as described above has the following significance in terms of operation and effect. The use of a steel sheet having surface irregularities within the above range means that the chromate layer and the organic resin film layer can be uniformly applied.

【0016】上述のような表面粗さを得るためには鋼板
をショットダル、レーザーダル等のロールで圧延処理す
る方法がある。Ra >0.13×Rz なる関係にある鋼板で
は鋼板表面の凸部で有機樹脂皮膜が薄いまたは形成され
ない状態となり、耐食性が低下する。さらに、クロメー
トが凹部に偏り電着塗装後の外観を劣化させる。また、
PPI が30未満の鋼板でも同様のことが言える。
In order to obtain the above-mentioned surface roughness, there is a method of rolling a steel sheet with rolls such as shot dull and laser dull. In a steel sheet having a relation of Ra> 0.13 × Rz, the organic resin film is thin or not formed at the projections on the steel sheet surface, and the corrosion resistance is reduced. Further, the chromate is biased toward the concave portion and deteriorates the appearance after the electrodeposition coating. Also,
The same is true for steel sheets with a PPI of less than 30.

【0017】さらに、どちらか一方のみを満たす場合も
同様のことが言え、耐食性および電着塗装性が低下す
る。そこで、鋼板Ra ≦0.13×Rz を満たし、かつPPI
が30以上のものを用いることとする。
Further, the same can be said when only one of them is satisfied, and the corrosion resistance and the electrodeposition coating property are reduced. Therefore, steel plate Ra ≦ 0.13 × Rz is satisfied and PPI
Is 30 or more.

【0018】第1層クロメート皮膜 クロメート皮膜の形成方法は、耐食性に特に優れている
塗装型クロメート皮膜が好ましい。すなわち、ロールコ
ーターをはじめとする慣用手段により塗布した後、80〜
250 ℃の温度で焼き付けるのが好ましい。
The method for forming the first layer chromate film is preferably a coating type chromate film which is particularly excellent in corrosion resistance. That is, after applying by a conventional means such as a roll coater, 80 to
Baking at a temperature of 250 ° C. is preferred.

【0019】クロメート皮膜の付着量は金属Cr量として
鋼板上の任意の5mm2 を測定し、0.1 μg以上であるこ
とが必要である。好ましくは0.2 〜0.6 μgである。Cr
量が0.1 μg以下では十分な耐食性が得られず、さら
に、電着塗装後の外観が劣化する。また0.6 μgを超え
ると、スポット溶接においてチップの損傷が激しくなる
場合がある。
The amount of the chromate film deposited must be 0.1 μg or more by measuring an arbitrary 5 mm 2 on the steel sheet as the amount of metallic Cr. Preferably it is 0.2 to 0.6 µg. Cr
When the amount is 0.1 μg or less, sufficient corrosion resistance cannot be obtained, and further, the appearance after electrodeposition coating is deteriorated. If it exceeds 0.6 μg, chip damage may be severe in spot welding.

【0020】クロメート液の組成としては、Cr3+/全Cr
[=Cr3+/(Cr3++Cr6+ )] の比を0.4 〜0.6 程度にする
のが好ましい。0.4 未満であると還元効率が劣り、0.6
を超えるとCr6+が過剰になり、処理液の安定性が損なわ
れる恐れがある。
The composition of the chromate solution is Cr 3+ / total Cr
It is preferable to set the ratio of [= Cr 3+ / (Cr 3+ + Cr 6+ )] to about 0.4 to 0.6. If it is less than 0.4, the reduction efficiency is poor, and 0.6
If it exceeds, Cr 6+ becomes excessive and the stability of the processing solution may be impaired.

【0021】また、耐食性向上を目的として所望により
乾性シリカをクロメート中に添加すると良い。この時、
Si/Crは0.1 未満ではSiO2添加の効果が見られず、2超
では溶接性の低下が心配されるため、Si/Crで0.1 〜2
のSiO2を含有するのが望ましい。
It is preferable to add desiccated silica to the chromate if desired for the purpose of improving corrosion resistance. At this time,
Si / Cr showed no effect of SiO 2 added is less than 0.1, since the decrease in weldability than 2 is concerned, 0.1-2 with Si / Cr
It is desirable to contain the SiO 2.

【0022】第2層有機樹脂皮膜 上述のように形成された第1層クロメート皮膜の上に、
有機樹脂皮膜を0.1 μm以上の厚みで設ける。好ましく
は0.1 〜2.0 μmである。0.1 μm未満では耐食性が不
十分となり、2.0 μmを超えると溶接性が低下する。
Second layer organic resin film On the first layer chromate film formed as described above,
Provide an organic resin film with a thickness of 0.1 μm or more. Preferably it is 0.1 to 2.0 μm. If it is less than 0.1 μm, the corrosion resistance becomes insufficient, and if it exceeds 2.0 μm, the weldability decreases.

【0023】この有機樹脂皮膜は、従来より塗装鋼板の
製造に使用されてきた各種の樹脂系被覆組成物を使用し
て形成することができる。有機樹脂皮膜は、装置が簡便
で造膜も速い熱硬化型皮膜が工業的には好ましいが、紫
外線または電子線硬化型皮膜や常温乾燥型皮膜とするこ
ともできる。
This organic resin film can be formed by using various resin-based coating compositions conventionally used for producing coated steel sheets. As the organic resin film, a thermosetting film which is simple in equipment and has a fast film formation is industrially preferable, but an ultraviolet or electron beam curable film or a room temperature drying film can also be used.

【0024】熱硬化型の有機樹脂皮膜は、架橋剤を含有
する樹脂液を塗布した後、適当な温度に加熱して塗膜を
焼き付けることにより形成される。好ましい樹脂種はエ
ポキシ系樹脂である。
The thermosetting organic resin film is formed by applying a resin solution containing a cross-linking agent and then heating the film to an appropriate temperature to bake the film. A preferred resin type is an epoxy resin.

【0025】塗布に用いる樹脂液中には、樹脂および架
橋剤の他に、必要により希釈用の溶媒や、1種もしくは
2種以上の添加剤を含有していてもよい。このような任
意の添加剤としては、無機充填剤、顔料類 (防錆顔料、
体質顔料、特に着色顔料) 、可塑剤、潤滑性付与成分な
どがある。
The resin liquid used for coating may contain a diluting solvent and one or more additives, if necessary, in addition to the resin and the crosslinking agent. Such optional additives include inorganic fillers, pigments (rust-proof pigments,
Extender, especially a coloring pigment), a plasticizer, a lubricity-imparting component, and the like.

【0026】好ましい樹脂種であるエポキシ系樹脂とし
ては、ビスフェノールA系、ビスフェノールF系、ノボ
ラック型、臭素化エポキシ等の任意のグリシジルエーテ
ル系エポキシ樹脂が使用できる。また、エポキシ樹脂中
のエポキシ基およびヒドロキシル基を乾性油脂肪酸中の
カルボキシル基と反応させたエポキシエステル樹脂、イ
ソシアネートと反応させることにより得られるウレタン
変性エポキシ樹脂などの変性エポキシ樹脂も使用でき
る。
As the epoxy resin, which is a preferred resin type, any glycidyl ether epoxy resin such as bisphenol A, bisphenol F, novolak, or brominated epoxy can be used. Further, modified epoxy resins such as an epoxy ester resin obtained by reacting an epoxy group and a hydroxyl group in an epoxy resin with a carboxyl group in a drying oil fatty acid, and a urethane modified epoxy resin obtained by reacting with an isocyanate can also be used.

【0027】また、本発明においてエポキシ樹脂の1種
として好適に使用できるものに、ポリヒドロキシポリエ
ーテル樹脂がある。この樹脂は、単核型もしくは二核型
の2価フェノールもしくは単核型と二核型との混合2価
フェノールを、アルカリ触媒の存在下にほぼ等モル量の
エピハロヒドリンと重縮合させて得られる重合体であ
る。
In the present invention, a polyhydroxypolyether resin is preferably used as one type of epoxy resin. This resin is obtained by polycondensing mononuclear or binuclear dihydric phenol or a mixture of mononuclear and dinuclear dihydric phenols with an approximately equimolar amount of epihalohydrin in the presence of an alkali catalyst. It is a polymer.

【0028】エポキシ系樹脂液中には、皮膜の種々の性
能 (例、加工性、可撓性、潤滑性、電着塗装性など) を
改善する目的で、エポキシ系以外の樹脂を添加してもよ
い。例えば、皮膜に可撓性を与えるためのブチラール樹
脂の添加、電着塗装性を向上するための水溶性樹脂の添
加などである。エポキシ系以外の樹脂の添加量は、あま
り多くなると耐食性の低下を招くので、樹脂液中の全樹
脂固形分の50重量%以下とする。
In order to improve various properties of the film (eg, processability, flexibility, lubricity, electrodeposition coating property, etc.), a resin other than epoxy resin is added to the epoxy resin liquid. Is also good. For example, addition of a butyral resin for giving flexibility to a film, addition of a water-soluble resin for improving electrodeposition coating properties, and the like. If the amount of the non-epoxy resin is too large, the corrosion resistance is reduced. Therefore, the amount is set to 50% by weight or less of the total resin solids in the resin liquid.

【0029】エポキシ系樹脂用の架橋剤としては、フェ
ノール樹脂、アミノ樹脂、ポリアミド、アミノポリアミ
ド、アミン、ブロックイソシアネート、酸無水物などの
公知の各種の架橋剤を1種もしくは2種以上使用するこ
とができる。架橋剤を使用すると、皮膜の耐食性が一層
向上する。架橋剤の添加量は、エポキシ系樹脂中のエポ
キシ基とヒドロキシル基の合計量に対する架橋剤中の官
能基のモル比が0.1 〜2の範囲内が好ましい。
As the crosslinking agent for the epoxy resin, one or more known crosslinking agents such as a phenol resin, an amino resin, a polyamide, an aminopolyamide, an amine, a blocked isocyanate and an acid anhydride may be used. Can be. The use of a crosslinking agent further improves the corrosion resistance of the film. The amount of the crosslinking agent to be added is preferably within a range of 0.1 to 2 in a molar ratio of the functional group in the crosslinking agent to the total amount of the epoxy group and the hydroxyl group in the epoxy resin.

【0030】樹脂皮膜の耐食性向上を目的として所望に
より無機充填材を樹脂液中に添加してもよい。有用な無
機充填材の例としては、乾性シリカ、コロイダルシリ
カ、各種ケイ酸塩鉱物、アルミナ、炭酸カルシウム、リ
ン酸亜鉛、リン酸カルシウム、リンモリブデン酸亜鉛、
リンモリブデン酸アルミニウムなどが挙げられる。無機
充填剤の添加量は、樹脂固形分に対して1〜30重量%の
範囲内が好ましい。
If desired, an inorganic filler may be added to the resin solution for the purpose of improving the corrosion resistance of the resin film. Examples of useful inorganic fillers include fumed silica, colloidal silica, various silicate minerals, alumina, calcium carbonate, zinc phosphate, calcium phosphate, zinc phosphomolybdate,
Aluminum phosphomolybdate and the like can be mentioned. The addition amount of the inorganic filler is preferably in the range of 1 to 30% by weight based on the solid content of the resin.

【0031】顔料としては、高い防食性向上効果を示す
ことが知られているクロム酸ストロンチウム、クロム酸
亜鉛などの金属クロム酸塩系防錆顔料が耐食性向上の目
的に有効である。また、本発明の有機複合被覆が片面の
みに形成される場合には、最上層の樹脂皮膜に着色顔料
を含有させて皮膜を着色しておくと、表裏の識別が容易
となり、ユーザーの作業に好都合である。着色顔料とし
ては、酸化鉄、酸化チタン顔料、カーボンなどの無機系
顔料以外に、有機系顔料も使用可能である。
As the pigment, metal chromate-based rust preventive pigments such as strontium chromate and zinc chromate, which are known to exhibit a high effect of improving corrosion resistance, are effective for the purpose of improving corrosion resistance. Further, when the organic composite coating of the present invention is formed only on one side, if the film is colored by adding a coloring pigment to the uppermost resin film, the front and back sides can be easily identified, and the work of the user can be easily performed. It is convenient. As the coloring pigment, an organic pigment can be used in addition to an inorganic pigment such as iron oxide, titanium oxide pigment, and carbon.

【0032】上述した樹脂液をロールコーターなどの適
当な塗布手段でクロメート皮膜上に塗布し、加熱して塗
膜を硬化させ、有機樹脂皮膜を形成する。加熱温度は、
エポキシ系樹脂の場合で80〜250 ℃、好ましくは120 〜
200 ℃である。素地鋼板が焼付け硬化型の場合には、こ
の時の加熱温度も150 ℃以下が好ましい。
The above-mentioned resin solution is applied on the chromate film by a suitable application means such as a roll coater and the like, and the coating is cured by heating to form an organic resin film. The heating temperature is
80-250 ° C., preferably 120-250 ° C. for epoxy resin
200 ° C. When the base steel sheet is a bake hardening type, the heating temperature at this time is also preferably 150 ° C. or less.

【0033】[0033]

【実施例】表面粗さRz 、Ra およびPPIを種々変化
させた母材 (各種めっき鋼板) を用いて、表1、表2に
示す皮膜構成および皮膜組成の有機複合被覆鋼板を作製
した。
EXAMPLES Organic composite coated steel sheets having coating compositions and coating compositions shown in Tables 1 and 2 were prepared using base materials (various plated steel sheets) having variously changed surface roughnesses Rz , Ra and PPI.

【0034】このとき、クロメート処理には市販の塗布
型クロメート処理液を原液で用いた。また、有機樹脂皮
膜の形成は、ビスフェノールA型エポキシ樹脂65重量
部、フェノール樹脂型硬化剤15重量部、乾性シリカ15重
量部、潤滑成分5重量部をシクロヘキサノンに溶解し、
NV (不揮発成分) =20%に調製した樹脂液を用いて行っ
た。このようにして得られた有機複合被覆鋼板における
耐食性および電着塗装性を以下に示す方法で評価した。
At this time, a commercially available coating type chromate treatment solution was used as a stock solution for the chromate treatment. The organic resin film is formed by dissolving 65 parts by weight of a bisphenol A type epoxy resin, 15 parts by weight of a phenol resin type curing agent, 15 parts by weight of dry silica, and 5 parts by weight of a lubricating component in cyclohexanone.
The test was performed using a resin solution adjusted to NV (nonvolatile component) = 20%. The corrosion resistance and electrodeposition coating properties of the thus obtained organic composite coated steel sheet were evaluated by the following methods.

【0035】[耐食性]70mm×150 mmの試験片を切り出
し、この未加工の平板を脱脂剤 SD270TO (日本ペイント
社製) で45℃にて210 秒間浸漬脱脂し、水洗後、165 ℃
で25分間の空焼きを行った。次いで、下に示すサイクル
設定の複合腐食試験を行った。
[Corrosion Resistance] A 70 mm × 150 mm test piece was cut out, and the unprocessed flat plate was immersed and degreased at 45 ° C. for 210 seconds with a degreasing agent SD270TO (manufactured by Nippon Paint Co., Ltd.), washed with water, and then washed at 165 ° C.
For 25 minutes. Next, a composite corrosion test with the cycle setting shown below was performed.

【0036】[0036]

【数1】 (Equation 1)

【0037】評価は、上記の腐食サイクル試験を120 サ
イクル実施後、赤錆発生面積率(%)を次のような段階に
区分して評価した。 ◎:赤錆発生なし ○: 5%以下 △: 20%以下 ×: 30%以下 ××: 30%超。
After 120 cycles of the above-described corrosion cycle test were performed, the area ratio (%) of red rust occurrence was evaluated in the following stages. :: No red rust occurred ○: 5% or less △: 20% or less ×: 30% or less XX: Over 30%.

【0038】[電着塗装製]70mm×150 mmの試験片を切り
出し、この未加工の平板を、脱脂剤リドリン SD270TO
(日本ペイント社製) で脱脂し、フィキソジン5TO(日本
ペイント社製) で表面調整した後、グラノチン SD2500M
Z(日本ペイント社製) を用いて化成処理を行い、次い
で、M635 (日本ペイント社製) で厚さ20±1μmのカチ
オン電着塗装を施し、165 ℃で25分間焼き付けた。その
後、塗装外観で次のように評価した。 ○: 良好 △: 電着塗装むら弱 ×: 電着塗装むら強
[Production made by electrodeposition coating] A test piece of 70 mm × 150 mm was cut out, and this unprocessed flat plate was used as a degreasing agent Ridolin SD270TO.
(Nippon Paint Co., Ltd.), degreased, surface-adjusted with FIXODIN 5TO (Nippon Paint Co., Ltd.), and then granotin SD2500M
A chemical conversion treatment was performed using Z (manufactured by Nippon Paint Co., Ltd.), and then a cationic electrodeposition coating with a thickness of 20 ± 1 μm was performed using M635 (manufactured by Nippon Paint Co., Ltd.), followed by baking at 165 ° C. for 25 minutes. Thereafter, the appearance of the coating was evaluated as follows. :: Good △: Uneven electrodeposition coating ×: Strong electrodeposition coating

【0039】[0039]

【表1】 [Table 1]

【0040】[0040]

【表2】 [Table 2]

【0041】[0041]

【表3】 [Table 3]

【0042】[0042]

【発明の効果】本発明の有機複合被覆鋼板は、従来の有
機複合被覆鋼板にない高い耐食性および電着塗装性を兼
ね備えており、自動車、家電製品、建材用に有用であ
る。
The organic composite coated steel sheet of the present invention has both high corrosion resistance and electrodeposition coating properties not found in the conventional organic composite coated steel sheet, and is useful for automobiles, home appliances, and building materials.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6,DB名) C23C 22/00 - 22/86 B32B 15/08 C25D 13/00──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C23C 22/00-22/86 B32B 15/08 C25D 13/00

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 亜鉛めっきもしくは亜鉛系合金めっき鋼
板の少なくとも片面上に、第1層として鋼板上の任意の
5mm2 に、Cr付着量として0.1 μg以上のクロメート皮
膜を有し、その上層に第2層として0.1 μm以上の有機
樹脂皮膜を有する有機複合被覆鋼板であって、母材たる
前記めっき鋼板の中心線平均粗さRaと十点平均粗さR
z がRa ≦0.13×Rz なる関係を満たし、かつ、該めっ
き鋼板の下記表面粗度パラメータPPIが30以上である
ことを特徴とする耐食性および電着塗装性に優れた有機
複合被覆鋼板。 PPI:1インチ当たりの山の数。但し、しきい値をR
MAX の30%以上とする。
1. A galvanized or zinc-based alloy-plated steel sheet, on at least one side thereof, as a first layer, an arbitrary 5 mm 2 on the steel sheet, and a chromate film having a Cr adhesion amount of 0.1 μg or more. An organic composite coated steel sheet having an organic resin film of 0.1 μm or more as two layers, wherein a center line average roughness Ra and a ten-point average roughness R of the plated steel sheet as a base material are provided.
z satisfies Ra ≦ 0.13 × R z the relationship, and, organic composite coated steel sheet excellent in corrosion resistance and electrodeposition paintability, characterized in that following surface roughness parameters PPI of the plated steel sheet is 30 or more. PPI: number of peaks per inch. However, the threshold is R
30% or more of MAX .
JP6258357A 1994-10-24 1994-10-24 Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties Expired - Fee Related JP2797983B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6258357A JP2797983B2 (en) 1994-10-24 1994-10-24 Organic composite coated steel sheet with excellent corrosion resistance and electrodeposition coating properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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Publication Number Publication Date
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JP2797983B2 true JP2797983B2 (en) 1998-09-17

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* Cited by examiner, † Cited by third party
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DE10064733A1 (en) * 2000-12-22 2002-07-11 Doerken Ewald Ag Piece of material, refined with a zinc coating and with applied electro-dip lacquer, and process for its production
TWI303672B (en) * 2002-07-29 2008-12-01 Jfe Steel Corp Coated steel sheet provided with electrodeposition painting having superior appearance
WO2010035847A1 (en) * 2008-09-24 2010-04-01 Jfeスチール株式会社 Rust-proof steel sheet and method for producing the same
US9623632B2 (en) * 2009-02-04 2017-04-18 Umicore Process for coating discrete articles with a zinc-based alloyed layer and articles obtained therefrom
KR102098475B1 (en) * 2018-07-06 2020-04-07 주식회사 포스코 A Manufacturing Method of Surface-treated Zn-Ni Alloy Electroplated Steel Sheet Having Excellent Corrosion Resistivity and Paintability

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