JP2001003181A - Precoated steel sheet excellent in adhesion to coating film and corrosion resistance of worked part and small in environmental load - Google Patents
Precoated steel sheet excellent in adhesion to coating film and corrosion resistance of worked part and small in environmental loadInfo
- Publication number
- JP2001003181A JP2001003181A JP17585399A JP17585399A JP2001003181A JP 2001003181 A JP2001003181 A JP 2001003181A JP 17585399 A JP17585399 A JP 17585399A JP 17585399 A JP17585399 A JP 17585399A JP 2001003181 A JP2001003181 A JP 2001003181A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- layer
- weight
- corrosion resistance
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は塗装鋼板に関する。
さらに詳しくは、加工部の耐食性に優れ、環境負荷の大
きいとされるクロムを含まないため地球に優しく、建材
用や家電用として好適な塗装鋼板に関するものである。The present invention relates to a coated steel sheet.
More specifically, the present invention relates to a coated steel sheet which is excellent in corrosion resistance of a processed portion and does not contain chromium which is considered to have a large environmental load, is eco-friendly, and is suitable for building materials and home appliances.
【０００２】[0002]
【従来の技術】家電や建材などの分野で加工後に塗装を
するポスト塗装製品に代わって、プレコート鋼板と呼ば
れる加工前に塗装を施した製品の使用量が増えてきてい
る。一般に厳しい加工を施すと塗装がダメージを受けて
耐食性が低下することが知られているのでプレコート鋼
板は、美観を有しながら、加工性と耐食性を併せ持つ必
要がある。2. Description of the Related Art Instead of post-painted products that are painted after processing in the fields of home appliances and building materials, the use of prepainted products, which are called pre-coated steel sheets, are increasing. It is generally known that when severe processing is performed, the coating is damaged and the corrosion resistance is reduced. Therefore, the pre-coated steel sheet needs to have both workability and corrosion resistance while having an aesthetic appearance.
【０００３】このようなプレコート鋼板の例として、例
えば、特開平０８−１６８７２３号公報には、皮膜の構
造を規定することによって加工性と、耐汚染性、硬度に
優れたプレコート鋼板を得る技術が開示されている。ま
た、特開平０３−１００１８０号公報には、特定のクロ
メート処理液を用いることで端面耐食性を改善したプレ
コート鋼板が開示されている。As an example of such a pre-coated steel sheet, for example, Japanese Patent Application Laid-Open No. 08-168723 discloses a technique for obtaining a pre-coated steel sheet having excellent workability, stain resistance and hardness by defining the structure of a film. It has been disclosed. Japanese Patent Application Laid-Open No. 03-100180 discloses a precoated steel sheet in which the end face corrosion resistance is improved by using a specific chromate treatment solution.
【０００４】いずれにおいても、耐食性に優れるめっき
鋼板の上にクロメート処理と呼ばれる耐食性と密着性に
優れる下地処理を施し、その上に耐食性に優れるクロム
系防錆顔料を含む下塗り層を有し、さらにその上に着色
された上塗り層を有する構造をとっている。[0004] In any case, a plated steel sheet having excellent corrosion resistance is subjected to a base treatment called chromate treatment, which is excellent in corrosion resistance and adhesion, and an undercoat layer containing a chromium-based rust preventive pigment having excellent corrosion resistance is provided thereon. It has a structure having a colored overcoat layer thereon.
【０００５】[0005]
【発明が解決しようとする課題】これらクロメート処理
およびクロム系防錆顔料に含まれる６価のクロムは水溶
性であり、これが溶出することによって亜鉛系のめっき
鋼板の腐食を抑制する性質がある。例えば、厳しい加工
で塗膜が割れた場合でも、その部分の腐食を抑制するな
ど、非常に優れており、今日までクロメート処理とクロ
ム系防錆顔料は幅広くプレコート鋼板に使用されてきて
いる。The hexavalent chromium contained in these chromate-treated and chromium-based rust preventive pigments is water-soluble, and has the property of inhibiting the corrosion of zinc-based plated steel sheets by being eluted. For example, even when a coating film is cracked by severe processing, it is extremely excellent in that the corrosion of the portion is suppressed. To date, chromate treatment and chromium-based rust preventive pigments have been widely used for precoated steel sheets.
【０００６】しかしながら、クロメート処理およびクロ
ム系防錆顔料から溶出する可能性のある６価のクロムは
環境負荷が大きな物質であるため、最近ではクロムフリ
ーの下地処理、クロムフリーの防錆顔料に対する要望が
高まっている。そこで、本発明では、このような要望に
答え、加工部の耐食性に優れるクロムフリーで環境負荷
の小さいプレコート鋼板を提供する事を目的とする。However, hexavalent chromium which may be eluted from the chromate treatment and the chromium-based rust-preventive pigment is a substance having a large environmental load. Therefore, there has recently been a demand for a chromium-free base treatment and a chromium-free rust-preventive pigment. Is growing. In view of the above, an object of the present invention is to provide a chromium-free pre-coated steel sheet which is excellent in corrosion resistance of a processed portion and has a small environmental load in response to such a demand.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、各種めっ
き鋼板の塗装後の加工部耐食性を各種クロムフリー下地
処理と各種クロムフリープライマーの条件で様々な検討
を重ねた。その結果、鋼板の表面にＺｎ−Ｍｇ−Ａｌ合
金めっきまたはＺｎ−Ｍｇ−Ａｌ−Ｓｉ合金めっきを施
し、下地処理としてクロメート処理の代わりにタンニン
またはタンニン酸系処理を施し、その上にクロム系防錆
顔料の代わりにクロムフリー防錆顔料を有する塗膜を施
すことで、優れた塗膜密着性と加工部の耐食性を有する
環境負荷の小さいクロムフリープレコート鋼板を製造し
得ることを見いだして、本発明を完成するに至った。す
なわち、本発明の趣旨とするところは、以下のとおりで
ある。Means for Solving the Problems The inventors of the present invention have conducted various studies on the corrosion resistance of a processed portion of various plated steel sheets after coating under various chrome-free primer treatment conditions and various chrome-free primer conditions. As a result, the surface of the steel sheet is plated with Zn-Mg-Al alloy or Zn-Mg-Al-Si alloy, and as a base treatment, tannin or tannic acid-based treatment is applied instead of chromate treatment, and chromium-based protection is applied thereon. By applying a coating film having a chrome-free rust-preventive pigment instead of a rust pigment, it was found that a chrome-free pre-coated steel sheet with excellent environmental impact and excellent corrosion resistance of the processed part could be manufactured. The invention has been completed. That is, the gist of the present invention is as follows.
【０００８】（１）鋼板の表面に下層として、Ｍｇ：１
〜１０重量％、Ａｌ：２〜１９重量％を含有し、かつ、
ＭｇとＡｌが式：Ｍｇ（％）＋Ａｌ（％）≦２０％を満
たし、残部がＺｎよりなるＺｎ合金めっき層を有し、そ
の上に固形分として樹脂１００重量部、タンニンまたは
タンニン酸０．２〜５０重量部を含有する下地処理皮膜
層を有し、さらにその上に有機皮膜層を上層として有す
ることを特徴とする加工部の耐食性に優れ環境負荷の小
さい塗装鋼板。(1) As a lower layer on the surface of a steel sheet, Mg: 1
10 to 10% by weight, Al: 2 to 19% by weight, and
Mg and Al satisfy the formula: Mg (%) + Al (%) ≦ 20%, and the balance has a Zn alloy plating layer composed of Zn, on which 100 parts by weight of resin as solid content, tannin or tannic acid 0.1%. A coated steel sheet having an excellent corrosion resistance of a processed portion and a low environmental load, comprising a base treatment film layer containing 2 to 50 parts by weight, and further having an organic film layer as an upper layer thereon.
【０００９】（２）鋼板の表面に下層として、Ｍｇ：１
〜１０重量％、Ａｌ：２〜１９重量％、Ｓｉ：０．０１
〜２重量％を含有し、かつ、ＭｇとＡｌが式：Ｍｇ
（％）＋Ａｌ（％）≦２０％を満たし、残部がＺｎより
なるＺｎ合金めっき層を有し、その上に固形分として樹
脂１００重量部、タンニンまたはタンニン酸０．２〜５
０重量部を含有する下地処理皮膜層を有し、さらにその
上に有機皮膜層を上層として有することを特徴とする加
工部の耐食性に優れ環境負荷の小さい塗装鋼板。(2) As a lower layer on the surface of the steel sheet, Mg: 1
10 to 10% by weight, Al: 2 to 19% by weight, Si: 0.01
２2% by weight, and Mg and Al have the formula: Mg
(%) + Al (%) ≦ 20%, the balance having a Zn alloy plating layer composed of Zn, 100 parts by weight of resin as a solid content, tannin or tannic acid 0.2 to 5
A coated steel sheet having an excellent corrosion resistance of a processed portion and a small environmental load, having a base treatment film layer containing 0 parts by weight, and further having an organic film layer as an upper layer thereon.
【００１０】（３）下地処理皮膜層に固形分として、微
粒シリカ１０〜５００重量部をさらに含有することを特
徴とする、（１）および（２）記載の加工部の耐食性に
優れ環境負荷の小さい塗装鋼板。 （４）有機皮膜層が防錆顔料を含む下塗り層と着色され
た上塗り層からなる（１）〜（３）記載の加工部の耐食
性に優れ環境負荷の小さい塗装鋼板。(3) The processed part according to (1) or (2), which further comprises 10 to 500 parts by weight of finely divided silica as a solid content in the undercoating film layer, has excellent corrosion resistance and is environmentally friendly. Small painted steel plate. (4) The coated steel sheet according to (1) to (3), wherein the organic coating layer is composed of an undercoat layer containing a rust-preventive pigment and a colored overcoat layer, which has excellent corrosion resistance in the processed portion and has a small environmental load.
【００１１】（５）塗装鋼板のＺｎ合金めっき層の下に
Ｎｉめっき層を有することを特徴とする（１）〜（４）
に記載の加工部の耐食性に優れ環境負荷の小さい塗装鋼
板。(5) The coated steel sheet has a Ni plating layer under the Zn alloy plating layer (1) to (4).
A coated steel sheet with excellent corrosion resistance and low environmental load in the processed part described in 1.
【００１２】[0012]
【発明の実施の形態】以下に本発明を詳細に説明する。
本発明の塗装鋼板は鋼板上にＺｎ−Ｍｇ−Ａｌ合金めっ
き、Ｚｎ−Ｍｇ−Ａｌ−Ｓｉ合金めっきとタンニンまた
はタンニン酸系処理、および１層または２層からなる有
機被覆層を順次付与したものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The coated steel sheet of the present invention is one in which Zn-Mg-Al alloy plating, Zn-Mg-Al-Si alloy plating and tannin or tannic acid-based treatment, and one or two organic coating layers are sequentially applied on the steel sheet. It is.
【００１３】本発明の下地鋼板としては、Ａｌキルド鋼
板、Ｔｉ，Ｎｂなどを添加した極低炭素鋼板、およびこ
れらにＰ，Ｓｉ，Ｍｎなどの強化元素を添加した高強度
鋼等種々のものが適用できる。Ｚｎ−Ｍｇ−Ａｌめっき
層は、Ｍｇ１〜１０重量％、Ａｌ２〜１９重量％、かつ
ＭｇとＡｌが式、Ｍｇ（％）＋Ａｌ（％）≦２０、残部
がＺｎよりなるＺｎ合金めっき層である。As the base steel sheet of the present invention, there are various kinds such as an Al-killed steel sheet, an ultra-low carbon steel sheet added with Ti and Nb, and a high-strength steel added with reinforcing elements such as P, Si and Mn. Applicable. The Zn-Mg-Al plating layer is a Zn alloy plating layer in which Mg is 1 to 10% by weight, Al is 2 to 19% by weight, Mg and Al are represented by the formula, Mg (%) + Al (%) ≦ 20, and the balance is Zn. .
【００１４】Ｍｇの含有量を１〜１０重量％に限定した
理由は、１重量％未満では耐食性を向上させる効果が不
十分であるためであり、１０重量％を超えるとめっき層
が脆くなって密着性が低下するためである。Ａｌの含有
量を２〜１９重量％に限定した理由は、２重量％未満で
はめっき層が脆くなって密着性が低下するためであり、
１９重量％を超えると耐食性を向上させる効果が認めら
れなくなるためである。ＭｇとＡｌの含有量を式、Ｍｇ
（％）＋Ａｌ（％）≦２０に限定した理由は、めっき中
のＺｎ含有量が小さいと犠牲防食効果が小さくなり耐食
性が低下するためである。The reason why the content of Mg is limited to 1 to 10% by weight is that if it is less than 1% by weight, the effect of improving corrosion resistance is insufficient, and if it exceeds 10% by weight, the plating layer becomes brittle. This is because the adhesion is reduced. The reason for limiting the Al content to 2 to 19% by weight is that if it is less than 2% by weight, the plating layer becomes brittle and the adhesion decreases,
If the content exceeds 19% by weight, the effect of improving the corrosion resistance cannot be recognized. The content of Mg and Al is expressed by the formula, Mg
The reason for limiting to (%) + Al (%) ≦ 20 is that when the Zn content in the plating is small, the sacrificial corrosion protection effect is reduced and the corrosion resistance is reduced.
【００１５】Ｚｎ−Ｍｇ−Ａｌ−Ｓｉめっき層は、Ｍｇ
１〜１０重量％、Ａｌ２〜１９重量％、Ｓｉ０．０１〜
２重量％、かつＭｇとＡｌが式、Ｍｇ（％）＋Ａｌ
（％）≦２０、残部がＺｎよりなるＺｎ合金めっき層で
ある。Ｚｎ−Ｍｇ−Ａｌ−Ｓｉめっき層は、上記のＺｎ
−Ｍｇ−Ａｌめっき層の効果を維持しながら、それにＳ
ｉを所定量で添加した場合に耐食性が向上する効果を有
するものである。The Zn—Mg—Al—Si plating layer is made of Mg
1 to 10% by weight, Al 2 to 19% by weight, Si 0.01 to
2% by weight, and Mg and Al are represented by the formula, Mg (%) + Al
(%) ≦ 20, the balance being a Zn alloy plating layer composed of Zn. The Zn—Mg—Al—Si plating layer is made of the above Zn
-While maintaining the effect of the Mg-Al plating layer,
When i is added in a predetermined amount, it has an effect of improving corrosion resistance.
【００１６】Ｍｇの含有量を１〜１０重量％に限定した
理由は、１重量％未満では耐食性を向上させる効果が不
十分であるためであり、１０重量％を超えるとめっき層
が脆くなって密着性が低下するためである。Ａｌの含有
量を２〜１９重量％に限定した理由は、２重量％未満で
はめっき層が脆くなって密着性が低下するためであり、
１９重量％を超えると耐食性を向上させる効果が認めら
れなくなるためである。以上は、Ｚｎ−Ｍｇ−Ａｌめっ
き層の場合と同じである。Ｓｉの含有量を０．０１〜２
重量％に限定した理由は、０．０１重量％未満ではめっ
き中のＡｌと鋼板中のＦｅが反応しめっき層が脆くなっ
て密着性が低下するためであり、２重量％を超えると密
着性を向上させる効果が認められなくなるためである。
好ましくはＡｌ含有量の３％以上である。ＭｇとＡｌの
含有量を式、Ｍｇ（％）＋Ａｌ（％）≦２０に限定した
理由は、めっき中のＺｎ含有量が小さいと犠牲防食効果
が小さくなり耐食性が低下するためである。The reason why the content of Mg is limited to 1 to 10% by weight is that if it is less than 1% by weight, the effect of improving the corrosion resistance is insufficient, and if it exceeds 10% by weight, the plating layer becomes brittle. This is because the adhesion is reduced. The reason for limiting the Al content to 2 to 19% by weight is that if it is less than 2% by weight, the plating layer becomes brittle and the adhesion decreases,
If the content exceeds 19% by weight, the effect of improving the corrosion resistance cannot be recognized. The above is the same as the case of the Zn-Mg-Al plating layer. Si content of 0.01 to 2
The reason why the content is limited to 0.01% by weight is that if the content is less than 0.01% by weight, Al in the plating reacts with Fe in the steel sheet, and the plating layer becomes brittle and the adhesion decreases. This is because the effect of improving the density cannot be recognized.
Preferably, it is at least 3% of the Al content. The reason why the contents of Mg and Al are limited to the formula, Mg (%) + Al (%) ≦ 20, is that if the Zn content in the plating is small, the sacrificial anticorrosion effect is reduced and the corrosion resistance is reduced.
【００１７】めっき層中には、これ以外にＦｅ，Ｓｂ，
Ｐｂなどを単独あるいは複合で１重量％以内含有しても
よい。Ｚｎ−Ｍｇ−Ａｌめっき又はＺｎ−Ｍｇ−Ａｌ−
Ｓｉめっきの付着量については特に制約は設けないが、
耐食性の観点から１０ｇ／ｍ 2 以上、加工性の観点から
３５０ｇ／ｍ2 以下で有ることが望ましい。本発明にお
いて、めっき鋼板の製造方法については特に限定すると
ころはなく、通常の無酸化炉方式の溶融めっき法が適用
できる。下層としてＮｉプレめっきを施す場合も通常行
われているプレめっき方法を適用すればよく、プレＮｉ
めっきを施した後、無酸化あるいは還元雰囲気中で急速
低温加熱を行い、そののちに溶融めっきを行う方法等が
好ましい。In the plating layer, Fe, Sb,
Even if Pb or the like is contained alone or in a composite within 1% by weight
Good. Zn-Mg-Al plating or Zn-Mg-Al-
There is no particular limitation on the amount of Si plating attached,
10 g / m from the viewpoint of corrosion resistance TwoAbove, from the viewpoint of workability
350 g / mTwoIt is desirable to have the following. The present invention
However, the method for producing a plated steel sheet is particularly limited.
There are no rollers, and a normal non-oxidizing furnace hot-dip plating method is applied.
it can. Normally used when applying Ni pre-plating as the lower layer
It is sufficient to apply the pre-plating method described
After plating, rapid in non-oxidizing or reducing atmosphere
A method of performing low-temperature heating and then hot-dip plating
preferable.
【００１８】さらに、加工部の耐食性をさらに向上させ
る場合には、下層にＮｉめっき層を設けることができ
る。このプレＮｉめっき量は２ｇ／ｍ2 以下が好まし
い。２ｇ／ｍ2 を超えるとめっき密着性が劣化する。プ
レめっき量の下限は、０．２ｇ／ｍ2 が好ましい。めっ
き下層にＮｉめっき層を有する場合に加工部の耐食性が
良好となる理由は、めっき層−地鉄界面に生成したＮｉ
−Ａｌ−Ｆｅ−Ｚｎ化合物が一種のバインダーの役割を
果たすことによるものと考えられる。In order to further improve the corrosion resistance of the processed portion, a Ni plating layer can be provided as a lower layer. This pre-Ni plating amount is preferably 2 g / m 2 or less. If it exceeds 2 g / m 2 , the adhesion of plating deteriorates. The lower limit of the pre-plating amount is preferably 0.2 g / m 2 . The reason why the corrosion resistance of the processed portion is good when the Ni plating layer is provided as the lower layer is that Ni formed at the plating layer-base iron interface.
It is considered that the -Al-Fe-Zn compound serves as a kind of binder.
【００１９】本発明のプレコート鋼板に用いる下地処理
皮膜層は、樹脂、特に水性樹脂をベースとしてタンニン
またはタンニン酸を含むことを特徴としている。この下
地処理皮膜層とＺｎ−Ｍｇ−Ａｌ合金めっき層、Ｚｎ−
Ｍｇ−Ａｌ−Ｓｉ合金めっき層を組み合わせることによ
り相乗的に加工部の耐食性が向上する。本下地処理皮膜
層のタンニンまたはタンニン酸の役割は、めっき層と強
固に反応して密着することと、一方で樹脂、特に水性樹
脂とも密着することにある。タンニンまたはタンニン酸
と密着した樹脂、特に水性樹脂はその上に塗装される樹
脂と強固に密着し、その結果としてめっき鋼板と塗膜が
従来から使用されてきたクロメート処理を使用せずとも
強固に密着するようになったものと考えられる。また、
タンニンやタンニン酸そのものが樹脂、特に水性樹脂を
仲立ちとせずにめっき鋼板と塗膜の結合に関与している
部分も存在するものと考えられる。The undercoat film layer used in the precoated steel sheet of the present invention is characterized by containing tannin or tannic acid based on a resin, particularly an aqueous resin. The undercoat layer and the Zn-Mg-Al alloy plating layer, Zn-
By combining the Mg—Al—Si alloy plating layer, the corrosion resistance of the processed portion is synergistically improved. The role of tannin or tannic acid in the undercoating layer is to strongly react with and adhere to the plating layer and to adhere to a resin, particularly an aqueous resin. Resins that are in close contact with tannin or tannic acid, especially aqueous resins, are in close contact with the resin to be coated on them, and as a result, the coated steel sheet and coating film are strong without using the conventionally used chromate treatment. It is considered that they came into close contact. Also,
It is considered that there is a portion where tannin or tannic acid itself participates in bonding of the coated steel sheet and the coating film without mediating the resin, particularly the aqueous resin.
【００２０】本発明の下地処理皮膜層の水性樹脂として
は、水溶性樹脂のほか、本来水不溶性でありながらエマ
ルジョンやサスペンジョンのように水中に微分散された
状態になりうる樹脂を含めて言う。このような水性樹脂
として使用できるものは、例えば、ポリオレフィン系樹
脂、アクリルオレフィン系樹脂、ポリウレタン系樹脂、
ポリカーボネート系樹脂、エポキシ系樹脂、ポリエステ
ル系樹脂、アルキド系樹脂、フェノール系樹脂、その他
の熱硬化型樹脂が挙げられ、架橋可能な樹脂が望まし
い。特に好ましい樹脂は、アクリルオレフィン系樹脂、
ポリウレタン系樹脂、および両者の混合樹脂である。こ
れらの水性樹脂の２種類以上を混合あるいは重合して使
用しても良い。The aqueous resin of the undercoating film layer of the present invention includes, in addition to a water-soluble resin, a resin which is inherently insoluble in water but can be finely dispersed in water such as an emulsion or a suspension. Those that can be used as such an aqueous resin include, for example, a polyolefin resin, an acrylic olefin resin, a polyurethane resin,
Examples thereof include a polycarbonate resin, an epoxy resin, a polyester resin, an alkyd resin, a phenol resin, and other thermosetting resins, and a crosslinkable resin is preferable. Particularly preferred resins are acrylic olefin resins,
It is a polyurethane resin or a mixed resin of both. Two or more of these aqueous resins may be mixed or polymerized for use.
【００２１】タンニンやタンニン酸は、樹脂、特に水性
樹脂の存在下で、Ｚｎ−Ｍｇ−Ａｌ合金めっき、Ｚｎ−
Ｍｇ−Ａｌ−Ｓｉ合金めっきと塗膜の両者と強固に結合
し、塗膜の密着性を飛躍的に向上させ、ひいては加工部
の耐食性を向上させる。タンニンまたはタンニン酸とし
ては加水分解できるタンニンでも縮合タンニンでもよ
く、これらの一部が分解されたものでも良い。タンニン
およびタンニン酸は、ハマメタタンニン、五倍子タンニ
ン、没食子タンニン、ミロバロンのタンニン、ジビジビ
のタンニン、アルガロビラのタンニン、バロニアのタン
ニン、カテキンなど特に限定するものではなく、市販の
もの、例えば「タンニン酸：ＡＬ」（富士化学工業製）
などを使用することができる。The tannin or tannic acid can be prepared by plating Zn—Mg—Al alloy, Zn—Mg in the presence of a resin, especially an aqueous resin.
It is firmly bonded to both the Mg-Al-Si alloy plating and the coating film, dramatically improving the adhesion of the coating film, and thereby improving the corrosion resistance of the processed portion. The tannin or tannic acid may be a hydrolyzable tannin or a condensed tannin, or may be a partially decomposed tannin or tannin. The tannins and tannic acids are not particularly limited, such as hamametannin, quintuple tannin, gallic tannin, myrovalone tannin, dividibine tannin, argarovira tannin, baronia tannin, catechin, and the like. AL ”(Fuji Chemical Industries)
Etc. can be used.
【００２２】タンニンおよびタンニン酸の含有量は樹脂
１００重量部に対して、タンニンまたはタンニン酸０．
２〜５０重量部がよい。タンニンまたはタンニン酸の含
有量が０．２重量部未満ではこれらを添加した効果がみ
られず、塗膜密着性や加工部の耐食性が不十分である。
一方、５０重量部を越えると逆に耐食性が低下したり、
処理液を長期間貯蔵しておくとゲル化したりして問題が
ある。The content of tannin or tannic acid is 100 parts by weight of the resin, and tannin or tannic acid is contained in 0.1 part by weight.
The amount is preferably 2 to 50 parts by weight. When the content of tannin or tannic acid is less than 0.2 parts by weight, the effect of adding these is not seen, and the adhesion of the coating film and the corrosion resistance of the processed portion are insufficient.
On the other hand, if it exceeds 50 parts by weight, on the contrary, the corrosion resistance decreases,
If the treatment liquid is stored for a long time, there is a problem that the treatment liquid gels.
【００２３】さらに微粒シリカを添加すると耐擦り傷
性、塗膜密着性、耐食性が向上する。本発明において微
粒シリカとは、微細な粒径をもつために水中に分散させ
た場合に安定に水分散状ものである。このような微粒シ
リカとしては、ナトリウムなどの不純物が少なく、弱ア
ルカリ系のものであれば、特に限定されない。例えば、
「スノーテックスＮ」（日産化学工業社製）、「アデラ
イトＡＴ−２０Ｎ」（旭電化工業社製）などの市販のシ
リカなどを用いることができる。When fine silica is further added, scratch resistance, coating film adhesion and corrosion resistance are improved. In the present invention, finely divided silica is a water-dispersed substance that has a fine particle size and is therefore stably dispersed when dispersed in water. Such fine silica is not particularly limited as long as it has few impurities such as sodium and is a weak alkali type. For example,
Commercially available silica such as "Snowtex N" (manufactured by Nissan Chemical Industries, Ltd.) and "Adelite AT-20N" (manufactured by Asahi Denka Kogyo) can be used.
【００２４】微粒シリカの含有量は固形分換算で、樹脂
１００重量部に対して１０〜５００重量部であることが
好ましい。１０重量部未満では添加した効果が少なく、
５００重量部を越えると耐食性向上の効果が飽和して不
経済である。また、必要に応じて界面活性剤、防錆抑制
剤、発泡剤、顔料などを添加しても良い。さらに密着性
を向上させるために、エッチング性フッ化物を添加して
もよい、エッチング性フッ化物としては、例えば、フッ
化亜鉛四水和物、ヘキサフルオロケイ酸亜鉛六水和物な
どを使用することができる。同じく密着性を向上させる
目的でシランカップリング剤を添加しても良い。シラン
カップリング剤としては、例えば、γ−（２−アミノエ
チル）アミノプロピルトリメトキシシラン、γ−（２−
アミノエチル）アミノプロピルメチルジメトキシシラ
ン、アミノシラン、γ−メタクリロキシプロピルトリメ
トキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエ
チル）−γ−アミノプロピルトリメトキシシラン、γ−
グリシドキシプロピルトリメトキシシラン、γ−メルカ
プトプロピルトリメトキシシラン、メチルトリメトキシ
シラン、ビニルトリメトキシシラン、オクタデシルジメ
チル〔３−（トリメトキシシリル）プロピル〕アンモニ
ウムクロライド、γ−クロロプロピルメチルジメトキシ
シラン、γ−メルカプトプロピルメチルジメトキシシラ
ン、メチルトリクロロシラン、ジメチルジクロロシラ
ン、トリメチルクロロシランなどを挙げることができ
る。The content of the fine silica is preferably 10 to 500 parts by weight based on 100 parts by weight of the resin in terms of solid content. If the amount is less than 10 parts by weight, the added effect is small,
If it exceeds 500 parts by weight, the effect of improving the corrosion resistance is saturated, which is uneconomical. Further, a surfactant, a rust inhibitor, a foaming agent, a pigment and the like may be added as necessary. In order to further improve the adhesion, an etching fluoride may be added. As the etching fluoride, for example, zinc fluoride tetrahydrate, zinc hexafluorosilicate hexahydrate, or the like is used. be able to. Similarly, a silane coupling agent may be added for the purpose of improving adhesion. Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-
(Aminoethyl) aminopropylmethyldimethoxysilane, aminosilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ -Mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and the like.
【００２５】下地処理皮膜層の塗布方法は特別限定する
ものではなく、一般に公知の塗装方法、例えば、ロール
コート、エアースプレー、エアーレススプレー、浸漬な
どが適用できる。塗布後の乾燥・焼き付けは、樹脂の重
合反応や硬化反応を考慮して、熱風炉、誘導加熱炉、近
赤外線炉、等公知の方法あるいはこれらを組み合わせた
方法で行えばよい。また、使用する水性樹脂の種類によ
っては紫外線や電子線などによって硬化させることもで
きる。あるいは強制乾燥を用いずに自然乾燥してもよい
し、Ｚｎ−Ｍｇ−Ａｌ合金めっき鋼板、Ｚｎ−Ｍｇ−Ａ
ｌ−Ｓｉ合金めっき鋼板を予め加熱しておいて、その上
に塗布して自然乾燥してもよい。The method of applying the undercoating layer is not particularly limited, and generally known coating methods such as roll coating, air spray, airless spray, immersion and the like can be applied. The drying and baking after the application may be performed by a known method such as a hot blast furnace, an induction heating furnace, a near-infrared furnace, or a combination thereof in consideration of a polymerization reaction and a curing reaction of the resin. Further, depending on the type of the aqueous resin used, the resin can be cured by ultraviolet rays or electron beams. Alternatively, natural drying may be performed without using forced drying, or Zn-Mg-Al alloy-plated steel sheet, Zn-Mg-A
The l-Si alloy-plated steel sheet may be heated in advance, applied thereon, and air-dried.
【００２６】下地処理皮膜層の乾燥後の付着量は１０〜
３０００ｍｇ／ｍ2 が好適である。１０ｍｇ／ｍ2 未満
では密着性が劣り加工部の耐食性が不十分である。一
方、３０００ｍｇ／ｍ2 を越えると不経済であるばかり
か加工性も低下して耐食性も劣るようになる。本発明の
プレコート鋼板は下地処理したＺｎ−Ｍｇ−Ａｌ合金め
っき鋼板、Ｚｎ−Ｍｇ−Ａｌ−Ｓｉ合金めっき鋼板の上
に有機被覆層を有することを特徴としている。有機被覆
としてはポリオレフィン樹脂、アクリル樹脂、ウレタン
樹脂、エポキシ樹脂、ポリエステル樹脂、塩化ビニル樹
脂、フッ素系樹脂、ブチラール樹脂、ポリカーボネート
樹脂、フェノール樹脂などである。これらの混合物や共
重合物も使用できる。また、これらにイソシアネート樹
脂、アミノ樹脂、シランカップリング剤あるいはチタン
カップリング剤等を補助成分として併用することができ
る。本発明によるプレコート鋼板は加工後に補修をされ
ずにそのまま使用されるケースが多いので、厳しい加工
が施される用途では、ポリエステル樹脂をメラミンで架
橋する樹脂系、ポリエステル樹脂をウレタン樹脂（イソ
シアネート、イソシアネート樹脂）で架橋する樹脂系、
塩化ビニル樹脂系、フッ素樹脂系（溶剤可溶型、アクリ
ル樹脂との分散混合型）が望ましい。The amount of adhesion of the undercoat layer after drying is 10 to
3000 mg / m 2 is preferred. If it is less than 10 mg / m 2 , the adhesion is poor and the corrosion resistance of the processed part is insufficient. On the other hand, if it exceeds 3000 mg / m 2 , not only is it uneconomical, but also the workability is reduced and the corrosion resistance is poor. The precoated steel sheet of the present invention is characterized by having an organic coating layer on a Zn-Mg-Al alloy-plated steel sheet and a Zn-Mg-Al-Si alloy-plated steel sheet which have been subjected to a base treatment. Examples of the organic coating include polyolefin resin, acrylic resin, urethane resin, epoxy resin, polyester resin, vinyl chloride resin, fluorine resin, butyral resin, polycarbonate resin, and phenol resin. These mixtures and copolymers can also be used. In addition, an isocyanate resin, an amino resin, a silane coupling agent, a titanium coupling agent, or the like can be used together as an auxiliary component. Since the precoated steel sheet according to the present invention is often used as it is without repair after processing, in applications where severe processing is performed, a resin system in which a polyester resin is crosslinked with melamine, and a polyester resin is a urethane resin (isocyanate, isocyanate Resin-based resin,
Desirable are vinyl chloride resin-based and fluorine resin-based (solvent-soluble type, dispersion mixed type with acrylic resin).
【００２７】本発明の上記有機被覆層は着色を施し、こ
の上にさらなる塗装をしなくても、そのまま使用できる
特徴を有する。有機被覆層の着色は顔料や染料などによ
る。顔料としては、無機系、有機系、両者の複合系に関
わらず公知のものを使用することができ、チタン白、亜
鉛黄、アルミナ白、シアニンブルー、等のシアニン系顔
料、カーボンブラック、鉄黒、べんがら、黄色酸化鉄、
モリブデートオレンジ、ハンサイエロー、ピラゾロンオ
レンジ、アゾ系顔料、紺青、縮合多環系顔料、などが例
示できる。この他に、金属片・粉末・パール顔料、マイ
カ顔料、インジゴイド染料、硫化染料、フタロシアニン
染料、ジフェニルメタン染料、ニトロ染料、アクリジン
染料、等が挙げられる。有機被覆層中の顔料濃度は特に
限定されず、必要な色や隠蔽力によって決定すればよ
い。The organic coating layer of the present invention is characterized in that it is colored and can be used as it is without further coating. The coloring of the organic coating layer depends on pigments and dyes. Known pigments can be used regardless of whether they are inorganic, organic, or a composite of the two, and include cyanine pigments such as titanium white, zinc yellow, alumina white, and cyanine blue, carbon black, and iron black. , Red iron oxide, yellow iron oxide,
Examples include molybdate orange, Hansa yellow, pyrazolone orange, azo pigments, navy blue, condensed polycyclic pigments, and the like. In addition, metal fragments, powders, pearl pigments, mica pigments, indigoid dyes, sulfur dyes, phthalocyanine dyes, diphenylmethane dyes, nitro dyes, acridine dyes and the like can be mentioned. The pigment concentration in the organic coating layer is not particularly limited, and may be determined depending on the required color and hiding power.
【００２８】また、着色に直接関わらない顔料や添加物
成分、例えば、硫酸バリウム、炭酸カルシウム、カオリ
ンクレー、等の顔料、消泡剤、レベリング剤、分散補助
剤、等の添加剤、ポリエチレン系、ポリプロピレン系、
エステル系、パラフィン系、フッ素系などの有機ワック
ス成分、二流化モリブデンなどの無機ワックス成分、塗
料粘度を下げるための希釈剤、溶剤、水、等を加えるこ
とができる。Further, pigments and additive components which are not directly involved in coloring, for example, pigments such as barium sulfate, calcium carbonate, kaolin clay, etc., additives such as defoaming agents, leveling agents, dispersing aids, etc., polyethylene, Polypropylene,
An organic wax component such as an ester, paraffin or fluorine, an inorganic wax component such as molybdenum disulfide, a diluent for lowering the viscosity of the paint, a solvent, and water can be added.
【００２９】さらに必要に応じて防錆顔料を添加しても
よい、防錆顔料としては一般に公知のもの、例えばリ
ン酸亜鉛、リン酸鉄、リン酸アルミニウム、亜リン酸亜
鉛、等のリン酸系防錆顔料、モリブデン酸カルシウ
ム、モリブデン酸アルミニウム、モリブデン酸バリウ
ム、等のモリブデン酸系防錆顔料、酸化バナジウムな
どのバナジウム系防錆顔料、カルシウムシリケートな
どのシリケート系顔料、ストロンチウムクロメート、
ジンククロメート、カルシウムクロメート、カリウムク
ロメート、バリウムクロメートなどのクロメート系防錆
顔料、水分散シリカ、ヒュームドシリカ、等の微粒シ
リカなどを用いることができる。しかしのクロメート
系防錆顔料は環境上負荷が大きいため、これら以外を使
用することが望ましい。If necessary, a rust preventive pigment may be added. As the rust preventive pigment, generally known rust preventive pigments, for example, phosphoric acid such as zinc phosphate, iron phosphate, aluminum phosphate, zinc phosphite, etc. Rust-based pigments, molybdate-based rust-proof pigments such as calcium molybdate, aluminum molybdate, barium molybdate, vanadium-based rust-proof pigments such as vanadium oxide, silicate-based pigments such as calcium silicate, strontium chromate,
Chromate-based rust preventive pigments such as zinc chromate, calcium chromate, potassium chromate and barium chromate, and finely divided silica such as water-dispersed silica and fumed silica can be used. However, since the chromate-based rust-preventive pigment has a large environmental load, it is desirable to use other than these.
【００３０】着色された有機被覆層は公知の方法で下地
処理皮膜層の上に塗装される。例えば、ロールコータ
ー、カーテンコーター、静電塗装、スプレー塗装、浸漬
塗装などである。その後、熱風、誘導加熱、近赤外、遠
赤外、などの加熱によって乾燥・硬化される。有機被覆
層の樹脂が電子線や紫外線で硬化するものであればこれ
らの照射によって硬化される。これらの併用であっても
よい。The colored organic coating layer is applied on the undercoat layer by a known method. For example, there are a roll coater, a curtain coater, an electrostatic coating, a spray coating, a dip coating, and the like. Thereafter, drying and curing are performed by heating with hot air, induction heating, near-infrared rays, far-infrared rays, and the like. If the resin of the organic coating layer is curable by electron beams or ultraviolet rays, it is cured by these irradiations. These may be used in combination.
【００３１】着色された有機被覆層の膜厚は特に限定す
るものではないが、均一な外観を得るためには５μｍ以
上の乾燥膜厚があることが望ましい。膜厚の上限はない
が、コイルで連続的に塗装する場合は１回の塗装で乾燥
膜厚が５０μｍ程度であることが多い、切り板に断続的
に塗装する場合は焼き付けを緩やかな条件で行うことが
可能であり、この上限膜厚は２００μｍ程度まで上が
る。また、スプレー塗装などで１枚毎に処理する場合は
さらに上限の膜厚は上がる。Although the thickness of the colored organic coating layer is not particularly limited, it is desirable that the dried organic coating layer has a dry thickness of 5 μm or more in order to obtain a uniform appearance. There is no upper limit on the film thickness, but when coating continuously with a coil, the dry film thickness is often about 50 μm in a single coating. The upper limit of the film thickness is increased to about 200 μm. Further, when processing is performed on each sheet by spray coating or the like, the upper limit film thickness further increases.
【００３２】本発明のプレコート鋼板で下地処理皮膜層
と着色された有機層の間に、必要に応じて防錆顔料を添
加した皮膜層を下塗り層として有することができる。こ
の下塗り層は主に耐食性の向上を目的とするが、その他
に成形加工性、耐薬品性などのも考慮して設計される。
下塗り層を構成する樹脂としては、一般に公知の樹脂、
例えば、ポリエステル樹脂、ウレタン樹脂、アクリル樹
脂、エポキシ樹脂、メラミン樹脂などをそのままあるい
は組み合わせて使用できる。防錆顔料としては一般に公
知のもの、例えば、リン酸亜鉛、リン酸鉄、リン酸ア
ルミニウム、亜リン酸亜鉛、等のリン酸系防錆顔料、
モリブデン酸カルシウム、モリブデン酸アルミニウム、
モリブデン酸バリウム、等のモリブデン酸系防錆顔料、
酸化バナジウムなどのバナジウム系防錆顔料、カル
シウムシリケートなどのシリケート系顔料、ストロン
チウムクロメート、ジンククロメート、カルシウムクロ
メート、カリウムクロメート、バリウムクロメートなど
のクロメート系防錆顔料、水分散シリカ、ヒュームド
シリカ、等の微粒シリカなどを用いることができる。し
かしのクロメート系防錆顔料は環境上負荷が大きいた
め、これら以外を使用することが望ましい。In the precoated steel sheet of the present invention, a coating layer to which a rust-preventive pigment is added, if necessary, may be provided as an undercoat layer between the undercoating coating layer and the colored organic layer. The purpose of this undercoat layer is mainly to improve corrosion resistance, but it is also designed in consideration of molding workability, chemical resistance and the like.
As the resin constituting the undercoat layer, generally known resins,
For example, polyester resin, urethane resin, acrylic resin, epoxy resin, melamine resin, etc. can be used as they are or in combination. As rust preventive pigments, generally known ones, for example, phosphoric acid rust preventive pigments such as zinc phosphate, iron phosphate, aluminum phosphate, zinc phosphite,
Calcium molybdate, aluminum molybdate,
Molybdate-based rust preventive pigments such as barium molybdate,
Vanadium-based rust preventive pigments such as vanadium oxide, silicate-based pigments such as calcium silicate, strontium chromate, zinc chromate, calcium chromate, potassium chromate, chromate-based rust preventive pigments such as barium chromate, water-dispersed silica, fumed silica, etc. Fine silica or the like can be used. However, since the chromate-based rust-preventive pigment has a large environmental load, it is desirable to use other than these.
【００３３】防錆顔料の添加量は皮膜の固形分基準に１
〜４０重量％がよい。１重量％より少ないと耐食性の改
良が十分でなく、４０重量％を越えると加工性が低下し
て、加工時に有機被膜層の脱落が起こり、耐食性も劣る
ようになる。防錆顔料を含む下塗り層の膜厚は３０μｍ
以下が好適であり、３０μｍを越えると加工性が低下し
て、加工時に有機被膜層の脱落が起こり耐食性も劣るよ
うになる。The amount of the rust preventive pigment to be added is 1 based on the solid content of the film.
~ 40% by weight is good. If the amount is less than 1% by weight, the corrosion resistance is not sufficiently improved, and if it exceeds 40% by weight, the workability is reduced, the organic coating layer is dropped off during the processing, and the corrosion resistance becomes poor. The thickness of the undercoat layer containing the antirust pigment is 30 μm
The following is preferred. If it exceeds 30 μm, the workability is reduced, and the organic coating layer is dropped off during the processing, resulting in poor corrosion resistance.
【００３４】防錆顔料を含む下塗り層の塗布は一般に公
知の方法でできる。例えば、ロールコート、カーテンコ
ート、エアースプレー、エアーレススプレー、浸漬、刷
毛塗り、バーコートなどである。その後、熱風、誘導加
熱、近赤外、遠赤外、などの加熱によって乾燥・硬化さ
れる。有機被覆層の樹脂が電子線や紫外線で硬化するも
のであればこれらの照射によって硬化される。これらの
併用であってもよい。The undercoat layer containing the rust-preventive pigment can be applied by a generally known method. For example, roll coating, curtain coating, air spray, airless spray, dipping, brush coating, bar coating, and the like. Thereafter, drying and curing are performed by heating with hot air, induction heating, near-infrared rays, far-infrared rays, and the like. If the resin of the organic coating layer is curable by electron beams or ultraviolet rays, it is cured by these irradiations. These may be used in combination.
【００３５】[0035]
【実施例】以下、実施例により本発明を具体的に説明す
る。 （実施例１）まず、厚さ０．８ｍｍの冷延鋼板を準備
し、これに浴温４５０〜５５０℃で、それぞれＭｇ量、
Ａｌ量を変化させたＺｎ−Ｍｇ−Ａｌめっき浴、Ｍｇ
量、Ａｌ量、Ｓｉ量を変化させたＺｎ−Ｍｇ−Ａｌ−Ｓ
ｉめっき浴を使用し３秒溶融めっきを行い、Ｎ2 ワイピ
ングでめっき付着量を１３５ｇ／ｍ2 に調整した。得ら
れためっき鋼板のめっき層中組成を表１〜４に示す。な
お、一部の試料については、下層にＮｉプレめっき層を
施した。The present invention will be described below in detail with reference to examples. (Example 1) First, a cold-rolled steel sheet having a thickness of 0.8 mm was prepared, and a Mg amount,
Zn-Mg-Al plating bath with varied Al content, Mg
Zn-Mg-Al-S with different amounts of Al, Si
Hot-dip plating was performed for 3 seconds using an i-plating bath, and the coating weight was adjusted to 135 g / m 2 by N 2 wiping. Tables 1 to 4 show the composition in the plating layer of the obtained plated steel sheet. In addition, about some samples, the Ni pre-plating layer was applied to the lower layer.
【００３６】めっき鋼板は、脱脂剤として日本パーカラ
イジング（株）製ＦＣ−３６４Ｓを使用し、２重量％の
水溶液に、６０℃、１０秒間浸漬し、その後、水洗、乾
燥の工程で脱脂処理を行った。次いで、アクリルオレフ
ィン樹脂１００重量部に対しタンニン酸２．５重量部、
シリカ３０重量部含有させた下地処理材を塗布し、熱風
乾燥炉で乾燥して付着量２００ｍｇ／ｍ2 とした。乾燥
時の到達板温は１５０℃とした。タンニン酸としては
「タンニン酸ＡＬ」富士化学工業（株）製を使用した。
シリカとしては「スノーテックスＮ」（日産化学工業
製）を使用した。The plated steel sheet was immersed in a 2% by weight aqueous solution at 60 ° C. for 10 seconds, and then subjected to a degreasing treatment in a washing and drying process using FC-364S manufactured by Nippon Parkerizing Co., Ltd. as a degreasing agent. Was. Next, 2.5 parts by weight of tannic acid with respect to 100 parts by weight of the acrylic olefin resin,
An undercoating material containing 30 parts by weight of silica was applied and dried in a hot-air drying oven to obtain an adhesion amount of 200 mg / m 2 . The reached plate temperature during drying was 150 ° C. As the tannic acid, "tannic acid AL" manufactured by Fuji Chemical Industry Co., Ltd. was used.
"Snowtex N" (manufactured by Nissan Chemical Industries) was used as silica.
【００３７】次に、下塗り塗装として日本ペイント製Ｐ
６４１プライマー塗料（ポリエステル樹脂系）の防錆顔
料を表１〜４に記載した防錆顔料（亜リン酸亜鉛、カル
シウムシリケート、バナジン酸／リン酸混合系、モリブ
デン酸系）に変更したものをバーコーターで塗布し、熱
風乾燥炉で最高到達板温が２２０℃となる条件で焼き付
けて膜厚を５μｍになるように調整した。下塗り塗装の
上に、上塗り塗装として、日本ペイント製ＦＬ１００Ｈ
Ｑ（ポリエステル樹脂系）をバーコーターで塗布し、熱
風乾燥炉で到達板温が２２０℃となる条件で焼き付けて
膜厚を１５μｍに調整した。Next, Nippon Paint P
The rust-preventive pigment of the 641 primer paint (polyester resin type) was changed to a rust-preventive pigment (zinc phosphite, calcium silicate, vanadic acid / phosphoric acid mixed type, molybdic acid type) described in Tables 1-4. The film was coated with a coater and baked in a hot-air drying oven under the condition that the maximum reached plate temperature was 220 ° C., so that the film thickness was adjusted to 5 μm. Nippon Paint FL100H as a top coat on top of the base coat
Q (polyester resin) was applied with a bar coater, and baked in a hot air drying furnace under the condition that the reached plate temperature was 220 ° C., to adjust the film thickness to 15 μm.
【００３８】以上のようにして作製した塗装鋼板に対し
て３Ｔ折り曲げ加工（原板を３枚はさんだ状態で１８０
°の折り曲げ加工）を施し、加工部の塗膜密着性試験と
耐食性試験を行った。塗膜密着性試験は、加工部に粘着
テープを貼り付け、これを勢いよく剥離したときの粘着
テープへの塗膜の付着状況で評価した。評点は、試験し
た長さに対する付着した塗膜の長さの割合に基づき、０
％以上２％未満を５、２％以上５％未満を４、付着量が
５％以上３０％を３、３０％以上８０％未満を２、８０
％以上を１、として評点４以上を合格とした。The coated steel sheet produced as described above was bent by 3T (180 pieces with three original sheets sandwiched).
° bending process), and a coating film adhesion test and a corrosion resistance test of the processed portion were performed. In the coating film adhesion test, an adhesive tape was attached to the processed portion, and the adhesion state of the coating film to the adhesive tape when this was vigorously peeled off was evaluated. The rating is based on the ratio of the length of the applied coating to the length tested, and is 0%.
% To less than 2% 5, 4, 2% to less than 5%, 3, 5% to 30% 3, and 30% to less than 80% 2,80
% Or more was 1, and a score of 4 or more was regarded as a pass.
【００３９】一方、耐食性の試験は、塩水噴霧（５％Ｎ
ａＣｌ，３５℃，２ｈｒ）→乾燥（６０℃，３０％Ｒ
Ｈ，４ｈｒ）→湿潤（５０℃，９５％ＲＨ，２ｈｒ）か
らなるサイクル腐食試験を１２０サイクル行った。サイ
クル腐食試験後に加工部の赤錆発生面積率を目視で観察
した。評点は、赤錆５％未満を５、赤錆５％以上１０％
未満を４、赤錆１０％以上２０％未満を３、２０％以上
３０％未満を２、３０％以上を１、として評点３以上を
合格とした。On the other hand, the corrosion resistance test was carried out using a salt spray (5% N
aCl, 35 ° C, 2 hr) → drying (60 ° C, 30% R)
H, 4 hr) → wet (50 ° C., 95% RH, 2 hr) was subjected to 120 cycle corrosion tests. After the cyclic corrosion test, the red rust generation area ratio of the processed portion was visually observed. The rating is 5 when red rust is less than 5%, and red rust is 5% or more and 10%.
A score of 3 or more was rated as 4 if less than 3, 3 if more than 10% and less than 20%, 2 if less than 20% and less than 30%, and 1 if more than 30%.
【００４０】総合評価は加工部の塗膜密着性と耐食性の
いずれもが合格点をクリアするものを合格（表中では○
と記載）とした。評価結果は表１〜４に示す通りであ
り、本発明材はいずれも良い塗膜密着性及び耐食性を示
した。表１〜４において、Ｍｇ，Ａｌを所定量含有する
本発明のＺｎ−Ｍｇ−Ａｌめっき層を形成した塗装鋼板
は、加工部の耐食性に優れていた。また、これらと同一
量のＭｇ，Ａｌと共に所定量のＳｉを含有するＺｎ−Ｍ
ｇ−Ａｌ−Ｓｉめっき層を形成した塗装鋼板の場合に
は、加工部の耐食性がＺｎ−Ｍｇ−Ａｌめっき層の場合
と比べても向上していることが認められる。一方、比較
例において、Ｍｇ，Ａｌの含有量が少なく、またＳｉも
含まないＺｎ合金めっき層の場合（Ｎｏ．３１）、耐食
性は低く、Ｍｇ，Ａｌ，Ｓｉを添加する場合でも、Ｍｇ
の含有量が少なすぎる場合（Ｎｏ．３２）、Ｍｇの含有
量が多すぎる場合（Ｎｏ．３３）、Ａｌの含有量が少な
すぎる場合（Ｎｏ．３４）、ＭｇとＡｌの合計量が多す
ぎる場合（Ｎｏ．３５）、およびＳｉの含有量が多すぎ
る場合（Ｎｏ．３６）には、いずれも、耐食性が十分で
はない。The overall evaluation was passed when both the coating film adhesion and the corrosion resistance of the processed portion passed the passing points (in the table, ○
Described). The evaluation results are as shown in Tables 1 to 4, and all the materials of the present invention showed good coating film adhesion and corrosion resistance. In Tables 1 to 4, the coated steel sheet having the Zn-Mg-Al plating layer of the present invention containing predetermined amounts of Mg and Al was excellent in the corrosion resistance of the processed portion. Further, Zn-M containing a predetermined amount of Si together with the same amounts of Mg and Al
In the case of the coated steel sheet having the g-Al-Si plating layer formed thereon, it is recognized that the corrosion resistance of the processed portion is improved as compared with the case of the Zn-Mg-Al plating layer. On the other hand, in the comparative example, in the case of a Zn alloy plating layer containing a small amount of Mg and Al and containing no Si (No. 31), the corrosion resistance was low, and even when Mg, Al, and Si were added,
Is too small (No. 32), the Mg content is too large (No. 33), the Al content is too small (No. 34), and the total amount of Mg and Al is too large. In both cases (No. 35) and when the content of Si is too large (No. 36), the corrosion resistance is not sufficient.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【表２】 [Table 2]
【００４３】[0043]
【表３】 [Table 3]
【００４４】[0044]
【表４】 [Table 4]
【００４５】（実施例２）まず、厚さ０．８ｍｍの冷延
鋼板を準備し、これに４５０℃のＺｎ−Ｍｇ−Ａｌめっ
き浴で３秒溶融めっきを行い、Ｎ2 ワイピングでめっき
付着量を１３５ｇ／ｍ2 に調整した。なお、下層にはＮ
ｉプレめっき層を施した。得られためっき鋼板のめっき
層中組成は、Ｍｇ３％、Ａｌ５％であった。Example 2 First, a cold-rolled steel sheet having a thickness of 0.8 mm was prepared, subjected to hot-dip plating in a Zn-Mg-Al plating bath at 450 ° C. for 3 seconds, and coated with N 2 wiping. Was adjusted to 135 g / m 2 . The lower layer is N
An i pre-plating layer was applied. The composition in the plating layer of the obtained plated steel sheet was Mg 3% and Al 5%.
【００４６】めっき鋼板は、脱脂剤として日本パーカラ
イジング（株）製ＦＣ−３６４Ｓを使用し、２重量％の
水溶液で、６０℃、１０秒間浸漬し、その後、水洗、乾
燥の工程で脱脂処理を行った。次いで、表２に示す組成
の下地処理材を塗布し熱風乾燥炉で乾燥した。乾燥時の
到達板温は１５０℃とした。タンニン酸としては「タン
ニン酸ＡＬ」富士化学工業（株）製、「ＢＲＥＷＴＡ
Ｎ」（オムニケム社製）、ＴＡＮＡＬ１（オムニケム社
製）を使用した。シリカとしては「スノーテックスＮ、
表中ではＳＴ−Ｎと記載」（日産化学工業製）を使用し
た。The plated steel sheet was immersed in a 2% by weight aqueous solution at 60 ° C. for 10 seconds, and then subjected to a degreasing treatment in a washing and drying process, using FC-364S manufactured by Nippon Parkerizing Co., Ltd. as a degreasing agent. Was. Next, a base material having the composition shown in Table 2 was applied and dried in a hot-air drying furnace. The reached plate temperature during drying was 150 ° C. As tannic acid, "tannic acid AL" manufactured by Fuji Chemical Industry Co., Ltd., "BREWTA
N "(manufactured by Omnichem) and TANAL1 (manufactured by Omnichem). As silica, "Snowtex N,
ST-N in the table "(manufactured by Nissan Chemical Industries, Ltd.).
【００４７】次に、下塗り塗装として日本ペイント製Ｐ
６４１プライマー塗料（ポリエステル樹脂系、表中の樹
脂種はポリエステルとした）、日本ペイント製Ｐ１０８
プライマー（エポキシ樹脂系、表中の樹脂種はエポキシ
とした）、日本ペイント製Ｐ３０４プライマー（ウレタ
ン樹脂系、表中の樹脂種はウレタンとした）の防錆顔料
を表２に記載した防錆顔料（亜リン酸亜鉛、カルシウム
シリケート、バナジン酸／リン酸混合系、モリブデン酸
系）に変更したものをバーコーターで塗布し、熱風乾燥
炉で最高到達板温が２２０℃となる条件で焼き付けて膜
厚を５μｍになるように調整した。下塗り塗装の上に、
上塗り塗装として、日本ペイント製ＦＬ１００ＨＱ（ポ
リエステル樹脂系）をバーコーターで塗布し、熱風乾燥
炉で到達板温が２２０℃となる条件で焼き付けて膜厚を
１５μｍに調整した。Next, Nippon Paint P
641 primer paint (polyester resin type, resin type in table is polyester), Nippon Paint P108
Rust preventive pigments described in Table 2 are primers (epoxy resin type, resin type in the table is epoxy), Nippon Paint P304 primer (urethane resin type, resin type in the table is urethane). (Zinc phosphite, calcium silicate, vanadic acid / phosphoric acid mixed system, molybdic acid system) is applied with a bar coater, and baked in a hot air drying furnace under the condition that the maximum temperature of the sheet reaches 220 ° C. The thickness was adjusted to 5 μm. On the undercoat,
As a top coat, FL100HQ (polyester resin) manufactured by Nippon Paint was applied using a bar coater, and baked in a hot-air drying oven under the condition that the reached plate temperature was 220 ° C., to adjust the film thickness to 15 μm.
【００４８】以上のようにして作製した塗装鋼板に対し
て３Ｔ折り曲げ加工（原板を３枚はさんだ状態で１８０
°の折り曲げ加工）を施し、加工部の塗膜密着性試験と
耐食性試験を行った。塗膜密着性試験は、加工部に粘着
テープを貼り付け、これを勢いよく剥離したときの粘着
テープへの塗膜の付着状況で評価した。評点は、試験し
た長さに対する付着した塗膜の長さの割合に基づき、０
％以上２％未満を５、２％以上５％未満を４、付着量が
５％以上３０％を３、３０％以上８０％未満を２、８０
％以上を１、として評点４以上を合格とした。The coated steel sheet produced as described above is bent by 3T (180 pieces with three original sheets sandwiched).
° bending process), and a coating film adhesion test and a corrosion resistance test of the processed portion were performed. In the coating film adhesion test, an adhesive tape was attached to the processed portion, and the adhesion state of the coating film to the adhesive tape when this was vigorously peeled off was evaluated. The rating is based on the ratio of the length of the applied coating to the length tested, and is 0%.
% To less than 2% 5, 4, 2% to less than 5%, 3, 5% to 30% 3, and 30% to less than 80% 2,80
% Or more was 1, and a score of 4 or more was regarded as a pass.
【００４９】一方、耐食性の試験は、塩水噴霧（５％Ｎ
ａＣｌ，３５℃，２ｈｒ）→乾燥（６０℃，３０％Ｒ
Ｈ，４ｈｒ）→湿潤（５０℃，９５％ＲＨ，２ｈｒ）か
らなるサイクル腐食試験を１２０サイクル行った。サイ
クル腐食試験後に加工部の赤錆発生面積率を目視で観察
した。評点は、赤錆５％未満を５、赤錆５％以上１０％
未満を４、赤錆１０％以上２０％未満を３、２０％以上
３０％未満を２、３０％以上を１、として評点３以上を
合格とした。On the other hand, the corrosion resistance test was carried out using a salt spray (5% N
aCl, 35 ° C, 2 hr) → drying (60 ° C, 30% R)
H, 4 hr) → wet (50 ° C., 95% RH, 2 hr) was subjected to 120 cycle corrosion tests. After the cyclic corrosion test, the red rust generation area ratio of the processed portion was visually observed. The rating is 5 when red rust is less than 5%, and red rust is 5% or more and 10%.
A score of 3 or more was rated as 4 if less than 3, 3 if more than 10% and less than 20%, 2 if less than 20% and less than 30%, and 1 if more than 30%.
【００５０】総合評価は加工部の塗膜密着性と耐食性の
いずれもが合格点をクリアするものを合格（表中では○
と記載）とした。評価結果を表５示す。本発明の条件で
作製した塗装鋼板は、いずれも従来のクロメート処理鋼
板（Ｎｏ．２５とＮｏ．２６）に近いレベルの塗膜密着
性と加工部耐食性を有している。下地処理皮膜層の上に
上塗り塗膜をもうけない場合（Ｎｏ．２２）はやや耐食
性が劣るが問題の無いレベルである。下地処理皮膜層の
タンニン含有量が少なすぎる場合（Ｎｏ．１５）は加工
部の密着性と耐食性が劣り、不適である。また、下地処
理皮膜層のタンニン酸含有量が多すぎる場合（Ｎｏ．１
７）も加工の際に塗膜の割れが大きくなり耐食性を落と
すので、不適である。Ｎｏ．２５とＮｏ．２６は塗膜密
着性と加工部耐食性のいずれにも優れるが環境上有害な
クロムを使用しているため不適である。In the overall evaluation, those in which both the coating film adhesion and the corrosion resistance of the processed portion passed the passing score were passed (in the table, ○
Described). Table 5 shows the evaluation results. Each of the coated steel sheets manufactured under the conditions of the present invention has a coating film adhesion level and a processed part corrosion resistance level near those of conventional chromate-treated steel sheets (No. 25 and No. 26). When an overcoat is not formed on the undercoating layer (No. 22), the corrosion resistance is slightly inferior, but at a level that does not cause any problem. When the tannin content of the undercoating layer is too low (No. 15), the adhesion and corrosion resistance of the processed portion are poor and are unsuitable. Further, when the tannic acid content of the undercoating film layer is too large (No. 1)
7) is also unsuitable, since the cracks in the coating film increase during processing and the corrosion resistance decreases. No. 25 and no. No. 26 is excellent in both the coating film adhesion and the corrosion resistance of the processed portion, but is unsuitable because chromium which is harmful to the environment is used.
【００５１】[0051]
【表５】 [Table 5]
【００５２】（実施例３）まず、厚さ０．８ｍｍの冷延
鋼板を準備し、これに４５０℃のＺｎ−Ｍｇ−Ａｌ−Ｓ
ｉめっき浴で３秒溶融めっきを行い、Ｎ2 ワイピングで
めっき付着量を１３５ｇ／ｍ2 に調整した。なお、下層
にはＮｉプレめっき層を施した。得られためっき鋼板の
めっき層中組成は、Ｍｇ３％，Ａｌ５％，Ｓｉ０．１５
％であった。Example 3 First, a cold-rolled steel sheet having a thickness of 0.8 mm was prepared, and Zn-Mg-Al-S
Hot-dip plating was performed for 3 seconds in an i-plating bath, and the amount of coating was adjusted to 135 g / m 2 by N 2 wiping. The lower layer was provided with a Ni pre-plating layer. The composition in the plating layer of the obtained plated steel sheet was Mg 3%, Al 5%, Si 0.15
%Met.
【００５３】めっき鋼板は、脱脂剤として日本パーカラ
イジング（株）製ＦＣ−３６４Ｓを使用し、２重量％の
水溶液とし、６０℃、１０秒間浸漬し、その後、水洗、
乾燥の工程で脱脂処理を行った。次いで、表２に示す組
成の下地処理材を塗布し熱風乾燥炉で乾燥した。乾燥時
の到達板温は１５０℃とした。タンニン酸としては「タ
ンニン酸ＡＬ」富士化学工業（株）製、「ＢＲＥＷＴＡ
Ｎ」（オムニケム社製）、ＴＡＮＡＬ１（オムニケム社
製）を使用した。シリカとしては「スノーテックスＮ、
表中ではＳＴ−Ｎと記載」（日産化学工業製）を使用し
た。The plated steel sheet was immersed in a 2% by weight aqueous solution using FC-364S manufactured by Nippon Parkerizing Co., Ltd. as a degreasing agent at 60 ° C. for 10 seconds.
A degreasing treatment was performed in a drying step. Next, a base material having the composition shown in Table 2 was applied and dried in a hot-air drying furnace. The reached plate temperature during drying was 150 ° C. As tannic acid, "tannic acid AL" manufactured by Fuji Chemical Industry Co., Ltd., "BREWTA
N "(manufactured by Omnichem) and TANAL1 (manufactured by Omnichem). As silica, "Snowtex N,
ST-N in the table "(manufactured by Nissan Chemical Industries, Ltd.).
【００５４】次に、下塗り塗装として日本ペイント製Ｐ
６４１プライマー塗料（ポリエステル樹脂系、表中の樹
脂種はポリエステルとした）、日本ペイント製Ｐ１０８
プライマー（エポキシ樹脂系、表中の樹脂種はエポキシ
とした）、日本ペイント製Ｐ３０４プライマー（ウレタ
ン樹脂系、表中の樹脂種はウレタンとした）の防錆顔料
を表２に記載した防錆顔料（亜リン酸亜鉛、カルシウム
シリケート、バナジン酸／リン酸混合系、モリブデン酸
系）に変更したものをバーコーターで塗布し、熱風乾燥
炉で最高到達板温が２２０℃となる条件で焼き付けて膜
厚を５μｍになるように調整した。下塗り塗装の上に、
上塗り塗装として、日本ペイント製ＦＬ１００ＨＱ（ポ
リエステル樹脂系）をバーコーターで塗布し、熱風乾燥
炉で到達板温が２２０℃となる条件で焼き付けて膜厚を
１５μｍに調整した。Next, Nippon Paint P
641 primer paint (polyester resin type, resin type in table is polyester), Nippon Paint P108
Rust preventive pigments described in Table 2 are primers (epoxy resin type, resin type in the table is epoxy), Nippon Paint P304 primer (urethane resin type, resin type in the table is urethane). (Zinc phosphite, calcium silicate, vanadic acid / phosphoric acid mixed system, molybdic acid system) is applied with a bar coater, and baked in a hot air drying furnace under the condition that the maximum temperature of the sheet reaches 220 ° C. The thickness was adjusted to 5 μm. On the undercoat,
As a top coat, FL100HQ (polyester resin) manufactured by Nippon Paint was applied using a bar coater, and baked in a hot-air drying oven under the condition that the reached plate temperature was 220 ° C., to adjust the film thickness to 15 μm.
【００５５】以上のようにして作製した塗装鋼板に対し
て３Ｔ折り曲げ加工（原板を３枚はさんだ状態で１８０
°の折り曲げ加工）を施し、加工部の塗膜密着性試験と
耐食性試験を行った。塗膜密着性試験は、加工部に粘着
テープを貼り付け、これを勢い良くはく離したときの粘
着テープへの塗膜の付着状況で評価した。評点は、試験
した長さに対する付着した塗膜の長さの割合に基づき、
０％以上２％未満を５、２％以上５％未満を４、付着量
が５％以上３０％を３、３０％以上８０％未満を２、８
０％以上を１、として評点４以上を合格とした。The coated steel sheet produced as described above was bent by 3T (180 pieces with three original sheets sandwiched).
° bending process), and a coating film adhesion test and a corrosion resistance test of the processed portion were performed. In the coating film adhesion test, an adhesive tape was attached to the processed portion, and the adhesion state of the coating film to the adhesive tape when this was peeled off vigorously was evaluated. The rating is based on the ratio of the length of the applied coating to the length tested,
0% or more to less than 2%, 5; 2% to less than 5%, 4; 5% to 30%, 3; 30% to less than 80%, 2,8
A score of 4 or more was regarded as pass, with 0% or more being 1.
【００５６】一方、耐食性の試験は、塩水噴霧（５％Ｎ
ａＣｌ，３５℃，２ｈｒ）→乾燥（６０℃，３０％Ｒ
Ｈ，４ｈｒ）→湿潤（５０℃，９５％ＲＨ，２ｈｒ）か
らなるサイクル腐食試験を１２０サイクル行った。サイ
クル腐食試験後に加工部の赤錆発生面積率を目視で観察
した。評点は、赤錆５％未満を５、赤錆５％以上１０％
未満を４、赤錆１０％以上２０％未満を３、２０％以上
３０％未満を２、３０％以上を１、として評点３以上を
合格とした。On the other hand, the corrosion resistance test was carried out using a salt spray (5% N
aCl, 35 ° C, 2 hr) → drying (60 ° C, 30% R)
H, 4 hr) → wet (50 ° C., 95% RH, 2 hr) was subjected to 120 cycle corrosion tests. After the cyclic corrosion test, the red rust generation area ratio of the processed portion was visually observed. The rating is 5 when red rust is less than 5%, and red rust is 5% or more and 10%.
A score of 3 or more was rated as 4 if less than 3, 3 if more than 10% and less than 20%, 2 if less than 20% and less than 30%, and 1 if more than 30%.
【００５７】総合評価は加工部の塗膜密着性と耐食性の
いずれもが合格点をクリアするものを合格（表中では○
と記載）とした。評価結果は表６に示す通りであり、表
５の結果とほぼ同様のことがいえ、本発明材はいずれも
良い耐食性を示した。In the overall evaluation, those in which both the coating film adhesion and the corrosion resistance of the processed portion clear the passing score were passed (in the table, ○).
Described). The evaluation results are as shown in Table 6, and it can be said that the results are almost the same as those in Table 5, and all the materials of the present invention showed good corrosion resistance.
【００５８】[0058]
【表６】 [Table 6]
【００５９】[0059]
【発明の効果】本発明により、環境負荷の大きなクロム
を含有せずに、加工部の耐食性に優れる塗装鋼板を提供
することが可能となる。According to the present invention, it is possible to provide a coated steel sheet which does not contain chromium, which has a large environmental load, and which has excellent corrosion resistance in the processed portion.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年８月２３日（２０００．８．２
３）[Submission date] August 23, 2000 (2008.2
3)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Correction target item name] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００８】（１）鋼板の表面に下層として、Ｍｇ：１
〜１０重量％、Ａｌ：４〜１９重量％を含有し、かつ、
ＭｇとＡｌが式：Ｍｇ（％）＋Ａｌ（％）≦２０％を満
たし、残部がＺｎよりなるＺｎ合金めっき層を有し、そ
の上に固形分として樹脂１００重量部、タンニンまたは
タンニン酸０．２〜５０重量部を含有する下地処理皮膜
層を有し、さらにその上に有機皮膜層を上層として有す
ることを特徴とする加工部の耐食性に優れ環境負荷の小
さい塗装鋼板。(1) As a lower layer on the surface of a steel sheet, Mg: 1
10 wt%, Al: contains 4-19% by weight, and,
Mg and Al satisfy the formula: Mg (%) + Al (%) ≦ 20%, and the balance has a Zn alloy plating layer composed of Zn, on which 100 parts by weight of resin as solid content, tannin or tannic acid 0.1%. A coated steel sheet having an excellent corrosion resistance of a processed portion and a low environmental load, comprising a base treatment film layer containing 2 to 50 parts by weight, and further having an organic film layer as an upper layer thereon.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１３】本発明の下地鋼板としては、Ａｌキルド鋼
板、Ｔｉ，Ｎｂなどを添加した極低炭素鋼板、およびこ
れらにＰ，Ｓｉ，Ｍｎなどの強化元素を添加した高強度
鋼等種々のものが適用できる。Ｚｎ−Ｍｇ−Ａｌめっき
層は、Ｍｇ１〜１０重量％、Ａｌ４〜１９重量％、かつ
ＭｇとＡｌが式、Ｍｇ（％）＋Ａｌ（％）≦２０、残部
がＺｎよりなるＺｎ合金めっき層である。As the base steel sheet of the present invention, there are various kinds such as an Al-killed steel sheet, an ultra-low carbon steel sheet added with Ti and Nb, and a high-strength steel added with reinforcing elements such as P, Si and Mn. Applicable. The Zn—Mg—Al plating layer is a Zn alloy plating layer in which Mg is 1 to 10% by weight, Al 4 to 19% by weight, and Mg and Al are represented by the formula, Mg (%) + Al (%) ≦ 20, and the balance is Zn. is there.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１４】Ｍｇの含有量を１〜１０重量％に限定した
理由は、１重量％未満では耐食性を向上させる効果が不
十分であるためであり、１０重量％を超えるとめっき層
が脆くなって密着性が低下するためである。Ａｌの含有
量を４〜１９重量％に限定した理由は、２重量％未満で
はめっき層が脆くなって密着性が低下することを考慮し
て、本発明の範囲を４重量％以上に限定するものである
が、１９重量％を超えると耐食性を向上させる効果が認
められなくなるためである。ＭｇとＡｌの含有量を式、
Ｍｇ（％）＋Ａｌ（％）≦２０に限定した理由は、めっ
き中のＺｎ含有量が小さいと犠牲防食効果が小さくなり
耐食性が低下するためである。The reason why the content of Mg is limited to 1 to 10% by weight is that if it is less than 1% by weight, the effect of improving corrosion resistance is insufficient, and if it exceeds 10% by weight, the plating layer becomes brittle. This is because the adhesion is reduced. The reason for limiting the Al content to 4 to 19% by weight is to consider that if the content is less than 2% by weight, the plating layer becomes brittle and the adhesion decreases.
Therefore, the scope of the present invention is limited to 4% by weight or more.
However, if it exceeds 19% by weight , the effect of improving the corrosion resistance cannot be recognized. The content of Mg and Al is expressed by the formula,
The reason for limiting to Mg (%) + Al (%) ≦ 20 is that if the Zn content in the plating is small, the sacrificial anticorrosion effect is reduced and the corrosion resistance is reduced.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４１[Correction target item name] 0041
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４１】[0041]
【表１】 [Table 1]
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４２[Correction target item name] 0042
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４２】[0042]
【表２】 [Table 2]
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４３[Correction target item name] 0043
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４３】[0043]
【表３】 [Table 3]
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４４[Correction target item name] 0044
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００４４】[0044]
【表４】 [Table 4]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金井 洋 千葉県富津市新富20−１ 新日本製鐵株式 会社技術開発本部内 (72)発明者 植田 浩平 千葉県富津市新富20−１ 新日本製鐵株式 会社技術開発本部内 (72)発明者 古川 博康 千葉県君津市君津１番地 新日本製鐵株式 会社君津製鐵所内 Ｆターム(参考） 4D075 AE03 CA13 CA33 DB05 DC10 EB07 EC03 EC15 4K044 AA02 AB02 BA01 BA10 BC02 CA53 4K062 AA01 BA08 BC13 BC15 FA12 GA08 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Kanai 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Inventor Kohei Ueda 20-1 Shintomi, Futtsu-shi, Chiba Made in New Japan (72) Inventor Hiroyasu Furukawa 1 Kimitsu, Kimitsu-shi, Chiba F-term in Kimitsu Works of Nippon Steel Corporation (Reference) BC02 CA53 4K062 AA01 BA08 BC13 BC15 FA12 GA08
Claims (5)
０重量％、Ａｌ：２〜１９重量％を含有し、かつ、Ｍｇ
とＡｌが式：Ｍｇ（％）＋Ａｌ（％）≦２０％を満た
し、残部がＺｎよりなるＺｎ合金めっき層を有し、その
上に固形分として樹脂１００重量部、タンニンまたはタ
ンニン酸０．２〜５０重量部を含有する下地処理皮膜層
を有し、さらにその上に有機皮膜層を上層として有する
ことを特徴とする加工部の耐食性に優れ環境負荷の小さ
い塗装鋼板。1. A method according to claim 1, wherein Mg: 1 to 1 as a lower layer on the surface of the steel sheet.
0% by weight, Al: 2 to 19% by weight, and Mg
And Al satisfy the formula: Mg (%) + Al (%) ≦ 20%, and the remainder has a Zn alloy plating layer composed of Zn, on which 100 parts by weight of resin as a solid content, tannin or tannic acid 0.2 A coated steel sheet having an excellent corrosion resistance of a processed portion and a small environmental load, having a base treatment film layer containing up to 50 parts by weight, and further having an organic film layer thereon.
０重量％、Ａｌ：２〜１９重量％、Ｓｉ：０．０１〜２
重量％を含有し、かつ、ＭｇとＡｌが式：Ｍｇ（％）＋
Ａｌ（％）≦２０％を満たし、残部がＺｎよりなるＺｎ
合金めっき層を有し、その上に固形分として樹脂１００
重量部、タンニンまたはタンニン酸０．２〜５０重量部
を含有する下地処理皮膜層を有し、さらにその上に有機
皮膜層を上層として有することを特徴とする加工部の耐
食性に優れ環境負荷の小さい塗装鋼板。2. As a lower layer on the surface of a steel sheet, Mg: 1-1.
0% by weight, Al: 2 to 19% by weight, Si: 0.01 to 2
% By weight, and Mg and Al have the formula: Mg (%) +
Zn that satisfies Al (%) ≦ 20% and the balance is Zn
An alloy plating layer, and a resin 100
The processed part has excellent corrosion resistance and environmental load, characterized by having an undercoating film layer containing 0.2 to 50 parts by weight of tannin or tannic acid, and further having an organic film layer thereon as an upper layer. Small painted steel plate.
リカ１０〜５００重量部をさらに含有することを特徴と
する、請求項１または２記載の加工部の耐食性に優れ環
境負荷の小さい塗装鋼板。3. The coated steel sheet according to claim 1 or 2, wherein the undercoating layer further contains 10 to 500 parts by weight of fine silica as a solid content. .
着色された上塗り層からなる請求項１〜３のいずれか１
項に記載の加工部の耐食性に優れ環境負荷の小さい塗装
鋼板。4. The method according to claim 1, wherein the organic coating layer comprises an undercoat layer containing a rust preventive pigment and a colored overcoat layer.
Painted steel sheet with excellent corrosion resistance and low environmental load in the processed part described in the item.
めっき層を有することを特徴とする請求項１〜４のいず
れか１項に記載の加工部の耐食性に優れ環境負荷の小さ
い塗装鋼板。5. The method according to claim 5, wherein Ni is provided under the Zn alloy plating layer of the coated steel sheet.
The coated steel sheet according to any one of claims 1 to 4, wherein the coated steel sheet has excellent corrosion resistance and a low environmental load.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17585399A JP3124266B2 (en) | 1999-06-22 | 1999-06-22 | Painted steel plate with excellent coating film adhesion and corrosion resistance of the processed part and low environmental load |
| US09/470,886 US6465114B1 (en) | 1999-05-24 | 1999-12-22 | -Zn coated steel material, ZN coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same |
| TW088122926A TWI236968B (en) | 1999-05-24 | 1999-12-24 | Plated steel material, plated steel sheet and coated steel sheet excellent in corrosion resistance, and a method of producing the same |
| PT99961441T PT1199376E (en) | 1999-05-24 | 1999-12-27 | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
| AU18030/00A AU758643B2 (en) | 1999-05-24 | 1999-12-27 | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
| EP99961441A EP1199376B1 (en) | 1999-05-24 | 1999-12-27 | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
| AT99961441T ATE362002T1 (en) | 1999-05-24 | 1999-12-27 | PLATED STEEL PRODUCT, PLATED STEEL SHEET AND PRE-COATED STEEL SHEET WITH EXCELLENT CORROSION RESISTANCE |
| DE69936071T DE69936071T2 (en) | 1999-05-24 | 1999-12-27 | PLATED STEEL PRODUCT, PLATED STEEL PLATE AND PRE-COATED STEEL PLATE WITH EXCELLENT CORROSION RESISTANCE |
| ES99961441T ES2283142T3 (en) | 1999-05-24 | 1999-12-27 | STEELED STEEL PRODUCTS, STEELED STEEL SHEET AND STEELED STEEL SHEET THAT HAS EXCELLENT CORROSION RESISTANCE. |
| PCT/JP1999/007362 WO2000071773A1 (en) | 1999-05-24 | 1999-12-27 | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
| CA002374757A CA2374757C (en) | 1999-05-24 | 1999-12-27 | Zn coated steel material.zn coated steel sheet and painted steel sheet excellent in corrosion resistance, and method of producing the same. |
| KR10-2001-7015025A KR100509626B1 (en) | 1999-05-24 | 1999-12-27 | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
| CNB998130958A CN1170955C (en) | 1999-05-24 | 1999-12-27 | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
| HK02106572.1A HK1044968B (en) | 1999-05-24 | 2002-09-06 | Zn coated steel sheet and painted steel excellent in corrosion resistance, and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17585399A JP3124266B2 (en) | 1999-06-22 | 1999-06-22 | Painted steel plate with excellent coating film adhesion and corrosion resistance of the processed part and low environmental load |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001003181A true JP2001003181A (en) | 2001-01-09 |
| JP3124266B2 JP3124266B2 (en) | 2001-01-15 |
Family
ID=16003355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17585399A Expired - Lifetime JP3124266B2 (en) | 1999-05-24 | 1999-06-22 | Painted steel plate with excellent coating film adhesion and corrosion resistance of the processed part and low environmental load |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3124266B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100629449B1 (en) | 2006-02-02 | 2006-09-27 | 기양금속공업(주) | Aluminium material of chemical coating method that use cr-free |
| KR20200129122A (en) | 2018-05-25 | 2020-11-17 | 닛폰세이테츠 가부시키가이샤 | Surface treatment steel plate |
| CN116547405A (en) * | 2021-12-03 | 2023-08-04 | 日本制铁株式会社 | Zn-based coated steel sheet |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4002534B2 (en) * | 2003-02-03 | 2007-11-07 | 新日本製鐵株式会社 | High corrosion-resistant coated steel sheet with excellent paint film adhesion and sharpness and low environmental impact |
| TWI701359B (en) * | 2018-05-25 | 2020-08-11 | 日商日本製鐵股份有限公司 | Surface treatment steel plate |
-
1999
- 1999-06-22 JP JP17585399A patent/JP3124266B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100629449B1 (en) | 2006-02-02 | 2006-09-27 | 기양금속공업(주) | Aluminium material of chemical coating method that use cr-free |
| KR20200129122A (en) | 2018-05-25 | 2020-11-17 | 닛폰세이테츠 가부시키가이샤 | Surface treatment steel plate |
| CN116547405A (en) * | 2021-12-03 | 2023-08-04 | 日本制铁株式会社 | Zn-based coated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3124266B2 (en) | 2001-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100740068B1 (en) | Conductive organic coatings | |
| CN100455699C (en) | Precoat metal plate excellent in press workability and method for production thereof | |
| KR20190076099A (en) | Coating composition for hot dip galvanized steel sheet having excellent corrosion-resistance and blackening-resistance the surface treated hot dip galvanized steel sheet prepared by using the coating composition and method for preparing the surface treated hot dip galvanized steel sheet | |
| JP4747625B2 (en) | Surface-treated steel sheet excellent in corrosion resistance and scratch resistance and method for producing the same | |
| JP2001089868A (en) | Substrate treating agent for precoated metallic sheet, coated substrate treated metallic sheet coated with the same and precoated metallic sheet excellent in working adhesion of coating film using the same | |
| JP3950370B2 (en) | Precoated metal sheet having excellent press formability and method for producing the same | |
| JP3124266B2 (en) | Painted steel plate with excellent coating film adhesion and corrosion resistance of the processed part and low environmental load | |
| JP4873974B2 (en) | Pre-coated metal plate and manufacturing method thereof | |
| JP2006321957A (en) | Aqueous surface-treating agent for environmental response type pre-coated metal material and surface-treating method | |
| JP3090207B1 (en) | Painted steel sheet with excellent corrosion resistance and low environmental load | |
| JP4319957B2 (en) | Pre-coated metal plate with excellent corrosion resistance | |
| JP3923418B2 (en) | Chromium-free galvanized steel sheet and its manufacturing method | |
| JP3833033B2 (en) | Pre-coated steel sheet with excellent corrosion resistance | |
| JP2010247347A (en) | Precoated cold-rolled steel sheet and method for manufacturing the same | |
| JP5979312B2 (en) | Pre-coated steel sheet and manufacturing method thereof | |
| JP4002534B2 (en) | High corrosion-resistant coated steel sheet with excellent paint film adhesion and sharpness and low environmental impact | |
| JP4246689B2 (en) | Pre-coated metal plate with excellent corrosion resistance | |
| JP2000265282A (en) | Precoated metallic sheet excellent in coating film adhesion and corrosion resistance | |
| JP2000218229A (en) | Low toxic coated steel sheet excellent in corrosion resistance of processed part | |
| JP2000248380A (en) | Production of non-chromium type treated galvanized steel sheet | |
| JP2003311877A (en) | Highly durable coated steel plate | |
| JP2000218228A (en) | Low toxic coated steel sheet excellent in corrosion resistance of processed part | |
| JP2000239861A (en) | Precoated steel sheet excellent in corrosion resistance | |
| JP2024048206A (en) | Painted steel plate | |
| JP2000167482A (en) | Precoated metal sheet having excellent adhesion property with coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20000919 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 3124266 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071027 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081027 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091027 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101027 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101027 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111027 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111027 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121027 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121027 Year of fee payment: 12 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131027 Year of fee payment: 13 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131027 Year of fee payment: 13 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |