JP3389884B2 - Surface treated steel sheet for fuel container and paint composition therefor - Google Patents
Surface treated steel sheet for fuel container and paint composition thereforInfo
- Publication number
- JP3389884B2 JP3389884B2 JP12740999A JP12740999A JP3389884B2 JP 3389884 B2 JP3389884 B2 JP 3389884B2 JP 12740999 A JP12740999 A JP 12740999A JP 12740999 A JP12740999 A JP 12740999A JP 3389884 B2 JP3389884 B2 JP 3389884B2
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- steel sheet
- resin layer
- resin
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガソリンを燃料と
する自動車の燃料容器 (燃料タンク) 用に適した、亜鉛
系めっき鋼板を素材とする表面処理鋼板に関し、特に腐
食性の高いギ酸等の有機酸を含んでいる、劣化したガソ
リンに対しても高い耐食性を示すと同時に溶接性にも優
れた表面処理鋼板、および該表面処理鋼板の製造に用い
られる塗料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated steel sheet made of a zinc-based plated steel sheet, which is suitable for a fuel container (fuel tank) of an automobile that uses gasoline as a fuel. The present invention relates to a surface-treated steel sheet containing an organic acid, which exhibits high corrosion resistance against deteriorated gasoline and is also excellent in weldability, and a coating material used for producing the surface-treated steel sheet.
【０００２】[0002]
【従来の技術】一般のガソリンを燃料とする自動車や二
輪車 (以下、自動車と総称) 用の燃料タンク用材料に
は、内外面の耐食性、特に内面側の燃料 (ガソリン) に
対する耐食性、プレス成形性、および溶接性が要求され
る。2. Description of the Related Art Fuel tank materials for general gasoline-fueled automobiles and two-wheeled vehicles (hereinafter collectively referred to as automobiles) have corrosion resistance on the inner and outer surfaces, particularly corrosion resistance on the inner surface fuel (gasoline) and press formability. , And weldability are required.
【０００３】このような性能を満たす燃料タンク用材料
として、従来はターンシートと呼ばれる、Pb−10〜25％
Sn合金めっき鋼板が広く使用されてきた。しかし、主に
環境問題から、人体に有害なPbを含有しない材料が求め
られるようになった。また、燃料に対する耐食性につい
ても、有機酸を含む劣化ガソリン環境での性能が求めら
れるなど、より高度なレベルが要求されている。As a fuel tank material satisfying such performances, conventionally referred to as turn sheet, Pb-10 to 25%
Sn alloy plated steel sheets have been widely used. However, mainly due to environmental problems, materials that do not contain Pb, which is harmful to the human body, have been demanded. Further, the corrosion resistance to fuel is required to be at a higher level such as the performance in a deteriorated gasoline environment containing an organic acid.
【０００４】この要請に対し、Alめっき鋼板 (例えば、
特開平９−156027号公報) 、Sn−Znめっき鋼板 (例え
ば、特開平８−269733号公報) などが代替品として開発
されている。このうち、Alめっき鋼板は、溶接やハンダ
付け等の接合性に問題があり、加工メーカー等での使い
勝手が向上した材料が望まれている。この点、Sn−約８
％Zn合金めっき鋼板は、性能的なバランスがよいとされ
ているが、めっきそのものの用途がほぼ燃料タンクに限
定されるため、市場規模が小さく、安定供給や価格面に
問題がある。従って、一般に広く用いられている、比較
的安価な亜鉛系めっき (即ち、Znめっき又はZn合金めっ
き) を燃料タンク用に適用することができれば、経済的
に有利である。In response to this request, an Al-plated steel sheet (for example,
JP-A-9-156027), Sn-Zn plated steel sheet (for example, JP-A-8-269733), and the like have been developed as alternatives. Among them, the Al-plated steel sheet has a problem in bondability such as welding and soldering, and a material having improved usability for processing manufacturers is desired. In this respect, Sn-about 8
% Zn alloy-plated steel sheets are said to have a good balance of performance, but since the application of plating itself is almost exclusively for fuel tanks, the market size is small, and there are problems in terms of stable supply and price. Therefore, it is economically advantageous if relatively inexpensive zinc-based plating (that is, Zn plating or Zn alloy plating), which is widely used, can be applied to the fuel tank.
【０００５】Zn系めっき鋼板を自動車用燃料タンク用途
に適用する技術としては、特開平10−137681号公報があ
る。この公報には、クロメート処理したZn系めっき鋼板
の上に、内面側にはNiおよびAl金属粉を含有するアミン
変性エポキシ樹脂層を被覆し、外面側にはワックスを含
有するシリカ含有樹脂層を被覆した表面処理鋼板が提案
されている。Japanese Patent Laid-Open No. 10-137681 discloses a technique for applying a Zn-plated steel sheet to a fuel tank for automobiles. In this publication, on a chromate-treated Zn-based plated steel sheet, the inner surface is coated with an amine-modified epoxy resin layer containing Ni and Al metal powder, and the outer surface is coated with a silica-containing resin layer containing wax. Coated surface treated steel sheets have been proposed.
【０００６】[0006]
【発明が解決しようとする課題】特開平10−137681号公
報に記載された表面処理鋼板では、樹脂層中のNiおよび
Al金属粉末により、タンク内部の耐食性を発現させてい
るが、皮膜の抵抗値が大きく、溶接性に劣るため、ユー
ザー (燃料タンクの製造者) での使い勝手が悪いことが
判明した。また、この公報では、無鉛ガソリン／500 pp
m ギ酸水溶液の１／１混合液、即ち、ギ酸濃度として25
0 ppm で内面耐食性を試験しているが、劣化ガソリン中
のギ酸濃度は1000 ppm程度に達することもあり、より高
度の内面耐食性が求められるようになってきている。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention In the surface-treated steel sheet described in JP-A-10-137681, Ni in the resin layer and
Although the Al metal powder exhibits corrosion resistance inside the tank, it has been found that it is not convenient for the user (manufacturer of the fuel tank) because the resistance of the film is large and the weldability is poor. In this publication, unleaded gasoline / 500 pp
m 1/1 formic acid aqueous solution, ie 25 as formic acid concentration
Although the internal corrosion resistance is tested at 0 ppm, the concentration of formic acid in deteriorated gasoline may reach about 1000 ppm, and higher internal corrosion resistance is required.
【０００７】Zn系めっき鋼板を使用して、経済的で、し
かも劣化した有機酸を含有するガソリンに対する高度の
耐食性 (以下、劣化ガソリン耐食性と称する) を備え、
さらに安定した溶接性を確保できる、低コストで性能バ
ランスのよい燃料タンク材料を得ることはこれまで容易
ではなかった。本発明は、このような燃料タンク材料を
開発することを課題とする。Using Zn-based plated steel sheet, it is economical and has a high degree of corrosion resistance to gasoline containing deteriorated organic acid (hereinafter referred to as deteriorated gasoline corrosion resistance),
It has not been easy so far to obtain a fuel tank material that can secure stable weldability and has a low cost and a good performance balance. The present invention aims to develop such a fuel tank material.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、素材とし
てZn系めっき鋼板を用いて、劣化ガソリン耐食性と溶接
性とを高度にバランスさせるべく鋭意検討した結果、Zn
系めっき鋼板の上層に、Ni、Al、Ni−Al合金から選んだ
金属顔料に加えて、さらにリン化鉄とフェロシリコンか
ら選んだ顔料を含有させた樹脂層を特定の付着量で形成
することにより、タンク内面の劣化ガソリン耐食性と溶
接性が良好な燃料容器用鋼板が得られることを見出し
た。[Means for Solving the Problems] As a result of diligent studies by the present inventors, a Zn-based plated steel sheet was used as a material to highly balance the deteriorated gasoline corrosion resistance and weldability.
To form a resin layer containing a pigment selected from iron phosphide and ferrosilicon, in addition to the metallic pigment selected from Ni, Al, and Ni-Al alloy, on the upper layer of the system-plated steel sheet with a specific adhesion amount. According to the above, it was found that a steel sheet for a fuel container having good corrosion resistance against deteriorated gasoline on the inner surface of the tank and weldability can be obtained.
【０００９】本発明は、亜鉛系めっき鋼板の少なくとも
片面の上層に、Ni、AlおよびNi−Al合金から選ばれた１
種もしくは２種以上の金属顔料Ａと、リン化鉄およびフ
ェロシリコンから選ばれた１種もしくは２種の顔料Ｂと
を、顔料Ａ／顔料Ｂの重量比が90／10〜30／70の範囲、
かつ顔料合計量が樹脂層の15〜70重量％の範囲となる量
で含有する熱硬化型樹脂層を３〜10 g/m2 の付着量で有
することを特徴とする、燃料容器用表面処理鋼板であ
る。According to the present invention, one selected from Ni, Al and Ni-Al alloys is provided as an upper layer on at least one surface of a zinc-based plated steel sheet.
One or more metal pigments A and one or two pigments B selected from iron phosphide and ferrosilicon, and the weight ratio of pigment A / pigment B is in the range of 90/10 to 30/70. ,
And a surface treatment for a fuel container, characterized in that it has a thermosetting resin layer contained in an amount such that the total amount of the pigment is in the range of 15 to 70% by weight of the resin layer, with an adhesion amount of 3 to 10 g / m 2. It is a steel plate.
【００１０】別の面からは、本発明は、樹脂と溶媒に加
えて、Ni、AlおよびNi−Al合金から選ばれた１種もしく
は２種以上の金属顔料Ａと、リン化鉄およびフェロシリ
コンから選ばれた１種もしくは２種の顔料Ｂとを含有す
る塗料組成物であって、顔料Ａ／顔料Ｂの重量比が90／
10〜30／70の範囲、かつ顔料合計量が該塗料組成物の固
形分重量に対して15〜70重量％の範囲となる量であるこ
とを特徴とする、燃料容器用表面処理鋼板の製造用塗料
組成物である。From another aspect, the present invention provides, in addition to a resin and a solvent, one or more metal pigments A selected from Ni, Al and Ni-Al alloys, iron phosphide and ferrosilicon. A coating composition containing one or two pigments B selected from the following, wherein the weight ratio of pigment A / pigment B is 90 /
Production of a surface-treated steel sheet for a fuel container, characterized in that it is in the range of 10 to 30/70 and the total amount of the pigment is in the range of 15 to 70% by weight based on the weight of the solid content of the coating composition. It is a coating composition.
【００１１】好ましくは、各顔料の平均粒径は 0.5〜15
μｍの範囲であり、樹脂層中の樹脂成分は変性エポキシ
樹脂である。Preferably, the average particle size of each pigment is 0.5 to 15
The resin component in the resin layer is a modified epoxy resin.
【００１２】[0012]
【発明の実施の形態】母材
めっき鋼板の母材としては、通常用いられている一般的
な冷延鋼板でよい。但し、燃料タンク用途の鋼板は一般
に厳しいプレス成形加工を受けるため、例えば、極低炭
素で、かつTi、Nb、Ｂが添加された成分系とすることが
好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Base material The base material of a plated steel sheet may be a general cold-rolled steel sheet that is normally used. However, since steel plates for fuel tanks are generally subjected to severe press forming, it is preferable to use, for example, a component system containing extremely low carbon and Ti, Nb, and B added.
【００１３】めっき
本発明の表面処理鋼板の素材は、経済性を考えて、比較
的安価で大量生産されている、Znめっき鋼板またはZn合
金めっき鋼板 (これらを、本発明では亜鉛系またはZn系
めっき鋼板と総称する) である。Zn合金めっきの例とし
ては、Zn−Al、Zn−Al−Si、Zn−Ni、Zn−Fe、Zn−Cr、
Zn−Co、Zn−Mg、Zn−Sn等が挙げられるが、これらに限
定されるものではない。なお、Zn合金は、Zn−55％Al合
金めっきのように、Znが50％をやや下回る (例、40〜50
％) 合金も包含する。めっき方法は、溶融めっき法、電
気めっき法、蒸着めっき法等のいずれでもよい。めっき
は、両面めっきが原則であるが、内面側だけの片面めっ
きとすることも不可能ではない。 Plating The raw material of the surface-treated steel sheet of the present invention is a Zn-plated steel sheet or a Zn-alloy-plated steel sheet (in the present invention, a zinc-based or Zn-based steel) which is relatively inexpensive and mass-produced in consideration of economy. It is collectively called a plated steel sheet). Examples of Zn alloy plating include Zn-Al, Zn-Al-Si, Zn-Ni, Zn-Fe, Zn-Cr,
Examples thereof include, but are not limited to, Zn-Co, Zn-Mg, and Zn-Sn. The Zn alloy has a Zn content of slightly less than 50% as in the case of Zn-55% Al alloy plating (e.g., 40 to 50%).
%) Including alloys. The plating method may be any of the hot dipping method, electroplating method, vapor deposition plating method and the like. In principle, double-sided plating is used, but single-sided plating on the inner surface side is not impossible.
【００１４】本発明で使用できるめっき鋼板の例として
は、電気Znめっき鋼板、溶融Znめっき鋼板、電気Zn合金
(例、Zn−Ni) めっき鋼板、溶融Zn合金 (例、Zn−Al)
合金めっき鋼板、合金化溶融Znめっき鋼板等がある。め
っき付着量は、耐食性の観点から、片面当たり10 g/m2
以上が好ましく、さらに好ましくは15 g/m2 以上であ
る。Examples of galvanized steel sheets that can be used in the present invention include electric Zn-plated steel sheets, hot-dip Zn-plated steel sheets and electric Zn alloys.
(Example, Zn-Ni) Plated steel sheet, molten Zn alloy (Example, Zn-Al)
Examples include alloy-plated steel sheets and alloyed hot-dip Zn-plated steel sheets. From the viewpoint of corrosion resistance, the coating weight is 10 g / m 2 per side.
It is preferably not less than 15 g / m 2 and more preferably not less than 15 g / m 2 .
【００１５】顔料含有樹脂層
上述したZn系めっき鋼板の少なくとも片面に、本発明に
従って顔料含有樹脂層を形成する。この樹脂層は、特に
劣化ガソリン耐食性に優れたものであるので、タンク内
面側に相当する片面だけに形成するのでもよいが、外面
側に対しても十分な耐食性を有しているので、両面とも
に本発明に従った顔料含有樹脂層を形成してもよい。 Pigment-Containing Resin Layer A pigment-containing resin layer is formed according to the present invention on at least one surface of the above Zn-plated steel sheet. Since this resin layer is particularly excellent in deteriorated gasoline corrosion resistance, it may be formed on only one surface corresponding to the inner surface of the tank, but since it has sufficient corrosion resistance also on the outer surface, Both may form a pigment-containing resin layer according to the present invention.
【００１６】内面用の樹脂の必要性能としては、内面の
劣化ガソリン耐食性、下地処理との密着性、および溶接
性である。これらの性能を全て高いレベルで満たすため
に、本発明では、Zn系めっき鋼板の上層に、Ni、Al、Ni
−Al合金から選ばれた１種または２種以上の金属顔料
(以下、顔料Ａ) と、リン化鉄とフェロシリコンから選
ばれた１種または２種の顔料 (以下、顔料Ｂ) とを含有
する樹脂層を、乾燥後の付着量が３〜10 g/m2 となるよ
うに形成する。従って、樹脂層の形成に使用する塗料組
成物は、樹脂と溶媒に加えて、この顔料Ａと顔料Ｂとを
含有する。The required performance of the resin for the inner surface is the deteriorated gasoline corrosion resistance of the inner surface, the adhesion to the surface treatment, and the weldability. In order to satisfy all of these performances at a high level, in the present invention, Ni, Al, Ni
-One or more metal pigments selected from Al alloys
A resin layer containing (hereinafter, pigment A) and one or two kinds of pigments selected from iron phosphide and ferrosilicon (hereinafter, pigment B) has an adhesion amount after drying of 3 to 10 g / It is formed to be m 2 . Therefore, the coating composition used for forming the resin layer contains the pigment A and the pigment B in addition to the resin and the solvent.
【００１７】樹脂層中の金属顔料Ａ、即ち、Ni粉、Al粉
およびNi−Al合金粉のうち、Ni粉は主に劣化ガソリン耐
食性の発現とある程度の溶接性の確保のために添加す
る。一方、Al粉は、劣化ガソリン耐食性の改善を目的と
して添加する。ガソリンが劣化してくると、ギ酸、酢酸
等の有機酸が発生し、腐食環境として厳しくなるが、こ
のような環境においてAl粉は特に有効である。Ni粉とAl
粉の両者を併用してもよい。Ni−Al合金粉を使用した場
合にも、Ni粉とAl粉を併用した場合と同様に、内面の劣
化ガソリン耐食性とある程度の溶接性とが得られる。The metal pigment A in the resin layer, that is, among the Ni powder, the Al powder and the Ni-Al alloy powder, the Ni powder is mainly added for the purpose of exhibiting deteriorated gasoline corrosion resistance and ensuring a certain weldability. On the other hand, Al powder is added for the purpose of improving corrosion resistance of deteriorated gasoline. When gasoline deteriorates, organic acids such as formic acid and acetic acid are generated, and the corrosive environment becomes severe, but Al powder is particularly effective in such an environment. Ni powder and Al
Both powders may be used together. Even when the Ni-Al alloy powder is used, the deteriorated gasoline corrosion resistance on the inner surface and a certain weldability can be obtained as in the case of using the Ni powder and the Al powder together.
【００１８】しかし、従来技術に関して説明したよう
に、樹脂層中に金属顔料Ａを配合しただけでは、樹脂層
の皮膜抵抗が大きすぎ、鋼板使用ユーザーが満足できる
使い勝手を与える、高度の溶接性を確保できない。そこ
で、本発明者らは、高度な溶接性を確保すべく、樹脂層
に含有させる顔料種について鋭意研究を重ねて、劣化ガ
ソリン耐食性を損なわずに、より高度のスポット溶接性
を確保するには、顔料Ａに加えて、リン化鉄および／ま
たはフェロシリコンからなる顔料Ｂを樹脂層に添加する
ことが有効であることを見いだした。However, as described in the prior art, only by mixing the metal pigment A in the resin layer, the film resistance of the resin layer is too large, and a high degree of weldability is provided, which gives the user of steel sheet satisfactory usability. Cannot be secured. Therefore, in order to ensure a high level of weldability, the present inventors have conducted extensive studies on the pigment species to be contained in the resin layer, in order to secure a higher level of spot weldability without impairing the deteriorated gasoline corrosion resistance. In addition to Pigment A, it was found effective to add Pigment B made of iron phosphide and / or ferrosilicon to the resin layer.
【００１９】顔料Ａと顔料Ｂの合計量は、樹脂層全体の
(従って、塗料組成物の固形分重量に対して) 15〜70重
量％、特に20〜50重量％を占める量とすることが好まし
い。15重量％未満では、十分な溶接性を確保することが
できない。一方、70重量％を超えると、鋼板表面への均
一な塗布が非常に困難になったり、顔料の量が多すぎ
て、プレス成形時に顔料の脱離が生じるため、成形性に
劣るようになる。The total amount of pigment A and pigment B is the total amount of the resin layer.
Therefore, it is preferable that the amount is 15 to 70% by weight, particularly 20 to 50% by weight, based on the solid content of the coating composition. If it is less than 15% by weight, sufficient weldability cannot be secured. On the other hand, if it exceeds 70% by weight, it becomes very difficult to apply it uniformly on the surface of the steel sheet, or the amount of the pigment is too large, and the pigment is detached during press molding, resulting in poor formability. .
【００２０】顔料Ａと顔料Ｂの割合は、劣化ガソリン耐
食性と溶接性を高度にバランスさせるために、顔料Ａ／
顔料Ｂの重量比が90／10〜30／70、特に90／10〜40／60
の範囲とすることが好ましい。この重量比が90／10より
大きくなると、顔料Ｂの量が少なすぎて、溶接性がやや
不足し、30／70より小さくなると、顔料Ａが少なすぎ
て、劣化ガソリン耐食性がやや不足する。The ratio of Pigment A to Pigment B is such that pigment A / Pigment A /
The weight ratio of pigment B is 90/10 to 30/70, especially 90/10 to 40/60
It is preferable to set it as the range. When the weight ratio is more than 90/10, the amount of the pigment B is too small and the weldability is slightly insufficient, and when it is less than 30/70, the pigment A is too small and the deteriorated gasoline corrosion resistance is slightly insufficient.
【００２１】本発明の樹脂層は、劣化ガソリンに含まれ
る腐食促進成分を鋼板から遮断する機能と、これまでに
説明した顔料のバインダとしての機能を果たすことが求
められる。従って、樹脂自体がガソリン成分に対して溶
解、膨潤もしくは透過を起こしにくい緻密な皮膜を形成
することが必要である。この目的に適した樹脂種は、架
橋により皮膜が緻密化する熱硬化性樹脂である。具体的
には、エポキシ系、アクリル系、ウレタン系、、ポリエ
ステル系、フェノール系樹脂等が適当な樹脂種として挙
げられる。The resin layer of the present invention is required to have the function of blocking the corrosion-promoting components contained in the deteriorated gasoline from the steel sheet and the function of the binder for the pigment described above. Therefore, it is necessary for the resin itself to form a dense film that is unlikely to dissolve, swell or permeate the gasoline component. A resin type suitable for this purpose is a thermosetting resin whose coating is densified by crosslinking. Specific examples of suitable resin species include epoxy-based, acrylic-based, urethane-based, polyester-based, and phenol-based resins.
【００２２】本発明で樹脂層に使用するのに特に適した
樹脂は、アミノ変性およびウレタン変性といった変性エ
ポキシ樹脂であり、中でもウレタン変性エポキシ樹脂が
好ましい。ウレタン変性エポキシ樹脂は、エポキシ樹脂
を二塩基酸と反応させてエポキシエステル樹脂とした
後、この樹脂の末端カルボキシル基をポリイソシアネー
ト化合物と反応させてウレタン化した樹脂である。得ら
れた樹脂は、エポキシ樹脂と同じ骨格を有し、末端の一
部がウレタン化されている。樹脂層のベース樹脂として
のウレタン変性エポキシ樹脂は、数平均分子量が約5000
〜50,000の範囲のものが好ましい。これより低分子量側
では、ガソリンに対して膨潤しやすくなり、高分子量側
のものは製造が困難であることのほかに、劣化ガソリン
に含まれる腐食促進成分の耐透過性にも劣る。Resins particularly suitable for use in the resin layer in the present invention are modified epoxy resins such as amino-modified and urethane-modified resins, and urethane-modified epoxy resins are particularly preferred. The urethane-modified epoxy resin is a resin obtained by reacting an epoxy resin with a dibasic acid to form an epoxy ester resin, and then reacting a terminal carboxyl group of this resin with a polyisocyanate compound to form a urethane. The obtained resin has the same skeleton as the epoxy resin, and a part of the terminal is urethanized. The urethane-modified epoxy resin as the base resin for the resin layer has a number average molecular weight of about 5,000.
Those in the range of up to 50,000 are preferred. On the lower molecular weight side, it tends to swell with respect to gasoline, and on the higher molecular weight side, it is difficult to manufacture, and the permeation resistance of the corrosion accelerating component contained in deteriorated gasoline is poor.
【００２３】ベース樹脂がエポキシ樹脂または変性エポ
キシ樹脂である場合には、硬化剤を使用する必要があ
る。適当な硬化剤の例としては、フェノール樹脂、メラ
ミン樹脂、ベンゾグアナミン樹脂等が例示される。劣化
ガソリン耐食性を考慮すると、より高分子量の樹脂層を
形成できるフェノール樹脂が硬化剤として好ましい。When the base resin is an epoxy resin or a modified epoxy resin, it is necessary to use a curing agent. Examples of suitable curing agents include phenolic resins, melamine resins, benzoguanamine resins and the like. Considering deteriorated gasoline corrosion resistance, a phenol resin capable of forming a resin layer having a higher molecular weight is preferable as a curing agent.
【００２４】（変性）エポキシ樹脂／硬化剤の重量比は
50／50〜98／２の範囲が好ましい。硬化剤が多すぎると
皮膜が硬く、脆くなり、加工性が低下する。硬化剤が少
なすぎると、硬化が十分に進行せず、耐劣化ガソリン性
が低下する。この重量比は、より好ましくは70／30〜90
／10、さらに好ましくは75／25〜85／15である。なお、
硬化剤を使用する場合、硬化剤の量も樹脂量の中に含め
る。硬化剤を配合した各種エポキシ樹脂液が市販されて
おり、それに上記の顔料ＡおよびＢを配合して、本発明
の樹脂層の形成に使用することができる。The weight ratio of (modified) epoxy resin / curing agent is
The range of 50/50 to 98/2 is preferable. If the amount of the curing agent is too much, the film becomes hard and brittle, and the workability is deteriorated. If the amount of the curing agent is too small, the curing will not proceed sufficiently and the deterioration gasoline resistance will deteriorate. This weight ratio is more preferably 70/30 to 90
/ 10, more preferably 75/25 to 85/15. In addition,
When a curing agent is used, the amount of the curing agent is also included in the resin amount. Various epoxy resin liquids containing a curing agent are commercially available, and the above-mentioned pigments A and B can be mixed therein and used for forming the resin layer of the present invention.
【００２５】この顔料Ａ、Ｂを含有する熱硬化性樹脂層
の付着量は、３〜10 g/m2 、好ましくは４〜７g/m2の範
囲とする。この付着量が３g/m2未満ではガソリン環境で
の耐食性に劣り、10 g/m2 を超えると効果が飽和し、コ
ストが上昇する上、本発明での顔料Ｂを用いても十分な
溶接性が得られないようになる。The adhesion amount of the pigment A, the thermosetting resin layer containing B is, 3~10 g / m 2, preferably in the range of 4~7g / m 2. If the amount of adhesion is less than 3 g / m 2 , the corrosion resistance in a gasoline environment is poor, and if it exceeds 10 g / m 2 , the effect is saturated and the cost increases, and even if the pigment B of the present invention is used, sufficient welding is achieved. You will not be able to get sex.
【００２６】本発明で樹脂層に含有させる上記顔料Ａお
よび顔料Ｂの粉末形状は特に制限されない。即ち、粒
状、鱗片状、針状、不規則形状等のいずれでもよい。各
顔料は、平均粒径 (粒状以外の場合は最大粒径の平均
値) が 0.5〜15μｍの範囲のものが良好である。樹脂層
の付着量が５g/m2以上となる場合には、より好ましく
は、平均粒径が、樹脂厚み (樹脂層の比重から算出する
か、ＳＥＭ等により実測することができる) の５〜150
％の範囲で、かつ上記の 0.5〜15μｍの範囲となること
がより好ましい。なお、樹脂層の付着量が３〜５g/m2の
場合も、顔料の平均粒径は、樹脂厚みの150 ％を超えな
いことが好ましい。顔料の平均粒径が小すぎると、樹脂
層の導電性が低下し、大きすぎると、溶接時の重ね合わ
せ部において顔料同士の物理的距離が遠くなるため、い
ずれも溶接性に劣る。The powder form of the above-mentioned pigment A and pigment B contained in the resin layer in the present invention is not particularly limited. That is, it may be granular, scale-shaped, needle-shaped, irregularly shaped, or the like. It is preferable that each of the pigments has an average particle diameter (an average value of maximum particle diameters other than those of particles) in the range of 0.5 to 15 μm. When the adhesion amount of the resin layer is 5 g / m 2 or more, more preferably, the average particle diameter is 5 to 5 of the resin thickness (calculated from the specific gravity of the resin layer or actually measured by SEM etc.). 150
%, And more preferably 0.5 to 15 μm. Even when the amount of the resin layer deposited is 3 to 5 g / m 2 , the average particle size of the pigment preferably does not exceed 150% of the resin thickness. If the average particle size of the pigment is too small, the conductivity of the resin layer is reduced, and if it is too large, the physical distance between the pigments becomes large at the overlapping portion during welding, and thus the weldability is poor.
【００２７】なお、Al粉の大きさは、化学作用による耐
食性改善効果の意味からは、特に規定されない。ただ
し、特開平10−137682号公報にあるように、10μｍ程度
の鱗片状の形状であると、物理的な遮蔽効果が期待され
るので、より好ましいと考えられる。The size of the Al powder is not particularly specified in terms of the effect of improving the corrosion resistance by the chemical action. However, as disclosed in Japanese Patent Laid-Open No. 10-137682, a scale-like shape having a size of about 10 μm is expected to have a physical shielding effect, and is considered to be more preferable.
【００２８】樹脂層中には、上記の導電顔料Ａと導電顔
料Ｂに加えて、任意成分として、例えば、着色顔料、防
錆顔料 (例、アルカリ土類金属クロム酸塩) 、他の導電
顔料、シリカ、シランカップリング剤等を、劣化ガソリ
ン耐食性、溶接性、加工性等の樹脂層の性能を著しく悪
化させない範囲で含有させることができる。In the resin layer, in addition to the above-mentioned conductive pigment A and conductive pigment B, as an optional component, for example, a coloring pigment, a rust preventive pigment (eg, alkaline earth metal chromate), or another conductive pigment. , Silica, a silane coupling agent, etc. can be contained in a range that does not significantly deteriorate the performance of the resin layer such as deteriorated gasoline corrosion resistance, weldability, and processability.
【００２９】樹脂層は、溶媒中に樹脂を溶解ないし分散
させた樹脂液中に導電顔料ＡおよびＢと所望により他の
成分を所定量づつ添加し、均一に分散または溶解させて
塗料組成物を調製し、この塗料組成物をめっき鋼板に塗
布した後、加熱して塗膜を焼付けて樹脂を硬化させるこ
とにより形成することができる。塗布法や焼付け温度は
特に制限されず、当業者であれば適当に選択できる。な
お、樹脂がウレタン変性エポキシ樹脂である場合の焼付
け温度は 170〜250 ℃の範囲が好ましい。塗料は、水系
塗料と溶剤系塗料のいずれでもよい。For the resin layer, the conductive pigments A and B and, if desired, other components are added in a predetermined amount to a resin solution prepared by dissolving or dispersing the resin in a solvent and uniformly dispersed or dissolved to form a coating composition. It can be formed by preparing and applying this coating composition to a plated steel sheet, followed by heating to bake the coating film to cure the resin. The coating method and baking temperature are not particularly limited and can be appropriately selected by those skilled in the art. When the resin is a urethane-modified epoxy resin, the baking temperature is preferably 170 to 250 ° C. The paint may be either water-based paint or solvent-based paint.
【００３０】その他
Zn系めっき鋼板に上記樹脂層を形成する前に、樹脂層の
密着性向上およびめっき鋼板の耐食性向上を目的とし
て、周知のクロメート処理やリン酸塩処理といった下地
処理を施すことは、本発明の効果をなんら減じるもので
はない。クロメート処理は、塗布型、反応型、電解型の
いずれの方式でもよい。下地処理は、付着量が大きすぎ
ると、溶接性を阻害する恐れがあるので、あまり過大に
しないことが好ましい。 Others Prior to forming the resin layer on the Zn-based plated steel sheet, a well-known base treatment such as chromate treatment or phosphate treatment may be performed for the purpose of improving the adhesion of the resin layer and the corrosion resistance of the plated steel sheet. However, the effect of the present invention is not reduced at all. The chromate treatment may be a coating type, a reaction type or an electrolytic type. If the amount of adhesion is too large, the base treatment may impair the weldability, so it is preferable not to make it too large.
【００３１】燃料タンク用途の鋼板は、一般に厳しいプ
レス成形加工を受けるので、プレス加工を支障なく行う
ため、特にタンク外面側の表面の潤滑性を高めることが
望ましい。そのため、本発明の樹脂層を鋼板の両面に形
成した場合には、特に外面側の上層に、固形潤滑剤の皮
膜を形成することができる。ただし、その後の外面の塗
装性が確保されることが必要で、アルカリ脱脂等で除去
される脱膜型の潤滑皮膜の方が、取り扱い上有利であ
る。また、内外両面の表面に防錆油を塗布したり、成形
加工時に潤滑油を塗布することもできる。Steel plates for use in fuel tanks are generally subjected to severe press forming work. Therefore, in order to carry out the press work without any trouble, it is desirable to enhance the lubricity of the surface of the outer surface of the tank. Therefore, when the resin layer of the present invention is formed on both surfaces of the steel sheet, a film of the solid lubricant can be formed especially on the outer surface side upper layer. However, it is necessary to secure the coatability of the outer surface thereafter, and a defilming type lubricating film that is removed by alkaline degreasing or the like is more advantageous in handling. Further, rust preventive oil can be applied to the inner and outer surfaces, and lubricating oil can be applied during molding.
【００３２】或いは、本発明の樹脂層を内面側の片面だ
けに形成し、外面側には他の樹脂皮膜、好ましくは潤滑
性 (成形性) と耐食性 (特に加工後耐食性) に優れた樹
脂皮膜とすることもできる。また、外面側はめっき (ま
たはめっき＋下地処理) のままとし、これに直接塗装を
施してもよい。Alternatively, the resin layer of the present invention is formed only on one surface on the inner surface side, and another resin film on the outer surface side, preferably a resin film excellent in lubricity (formability) and corrosion resistance (especially corrosion resistance after processing). Can also be Alternatively, the outer surface side may be left as it is as a plating (or as a plating + surface treatment) and may be directly coated.
【００３３】[0033]
【実施例】以下の実施例は本発明を例示するものであっ
て、本発明を制限する意図はない。なお、実施例中のめ
っき、下地処理、樹脂層の付着量は、いずれも片面当た
りの付着量である。The following examples are illustrative of the invention and are not intended to limit the invention. In addition, the plating amount, the base treatment, and the adhesion amount of the resin layer in the examples are all the adhesion amounts per one surface.
【００３４】(実施例１)両面Zn−13％Ni電気めっき鋼板
(めっき付着量30 g/m2)の両面に、塗布型クロメート処
理を、Cr付着量60 mg/m2となるように施した。(Example 1) Double-sided Zn-13% Ni electroplated steel sheet
Both sides of the (plating adhesion amount 30 g / m 2 ) were subjected to coating chromate treatment so that the Cr adhesion amount was 60 mg / m 2 .
【００３５】このクロメート処理Zn−Ni合金電気めっき
鋼板の片面に、数平均分子量30,000の熱硬化性ウレタン
変性エポキシ樹脂をベース樹脂とし、その樹脂液 (溶
媒：シクロヘキサノン) に表１に示す割合で下記顔料の
１種以上を分散させた塗料を、乾燥後の樹脂層の付着量
が６g/m2となるようにバーコータで塗布し、230 ℃で50
秒間焼き付けて、顔料含有樹脂層を形成した。On one side of this chromate-treated Zn-Ni alloy electroplated steel sheet, a thermosetting urethane-modified epoxy resin having a number average molecular weight of 30,000 was used as a base resin, and the resin solution (solvent: cyclohexanone) was used in the proportions shown in Table 1 below. Apply a paint in which one or more pigments are dispersed with a bar coater so that the adhesion of the resin layer after drying will be 6 g / m 2, and at 50 ° C at 230 ° C.
After baking for 2 seconds, a pigment-containing resin layer was formed.
【００３６】使用した顔料
Ni粉：平均粒径0.8 μｍの粒状
Al粉：平均粒径13μｍの鱗片状
Ni−Al合金粉：平均粒径３μｍの粒状
リン化鉄：平均粒径６μｍの粒状
フェロシリコン：平均粒径４μｍの粒状
こうして作成した、片面だけに樹脂層を有する表面処理
鋼板について、燃料タンク用途として必要な下記に示し
た特性に対する評価試験を行った。なお、いずれも評価
が「○」までが合格である。試験結果を、樹脂層の組成
と併せて、表１に示す。 Pigment used Ni powder: granular Al powder having an average particle size of 0.8 μm: scaly Ni-Al alloy powder having an average particle size of 13 μm: granular iron phosphide having an average particle size of 3 μm: granular ferrosilicon having an average particle size of 6 μm : Granular particles having an average particle diameter of 4 μm The surface-treated steel sheet having a resin layer formed on only one surface thereof was subjected to an evaluation test for the following characteristics required for fuel tank applications. In addition, in all cases, the evaluation is "○". The test results are shown in Table 1 together with the composition of the resin layer.
【００３７】試験方法
(1) 劣化ガソリン耐食性 (内面耐食性)
下記の絞り条件で、供試材の樹脂層を形成した面 (樹脂
面) が内面となるようにカップ絞りを行い、成形された
カップの中に、ギ酸3000 ppmの水溶液10 cc とガソリン
20 cc とを入れて密閉し（従って、試験液中のギ酸濃度
は1000 ppm) 、50℃に保持した。評価は、20日後の腐食
生成物 (液のにごり) 状況で、下記の通りに判定した。 Test method (1) Degraded gasoline corrosion resistance (inner surface corrosion resistance) Under the following drawing conditions, cup drawing was performed so that the surface of the test material on which the resin layer was formed (resin surface) was the inner surface, and a molded cup was formed. In a solution of 3000 ppm formic acid in water and 10 cc of gasoline
20 cc was added and the container was sealed (hence the concentration of formic acid in the test solution was 1000 ppm) and kept at 50 ° C. The evaluation was made as follows based on the state of corrosion products (liquid cloudiness) after 20 days.
【００３８】絞り条件 ブランク径：100 mm、 パンチ径：50 mm (5R)、 ダイス径：52.5 mm (5R)、 絞り高さ：25 mm、 潤滑油使用、絞り成形後にアルカリ脱脂。 Drawing conditions Blank diameter: 100 mm, punch diameter: 50 mm (5R), die diameter: 52.5 mm (5R), drawing height: 25 mm, using lubricating oil, alkaline degreasing after drawing.
【００３９】評価基準
◎ ：ほとんど変化なし；
○ ：上から見て10〜40％程度のにごり発生；
△ ：上から見て40〜70％程度のにごり発生(底面の観
察がかなり困難) ；
× ：ほぼ液全体に赤錆が浮遊 (底面、側面の観察がか
なり困難) 、またはカット部等から内面樹脂の剥離、膨
れが認められる。 Evaluation criteria ◎: Almost no change; ○: About 10 to 40% of turbidity seen from above; △: About 40 to 70% of turbidity seen from above (bottom observation is quite difficult); × : Red rust floats almost all over the liquid (observation of the bottom and sides is quite difficult), or peeling and swelling of the inner surface resin from the cut part.
【００４０】(2) 溶接性
２枚の供試材を、合わせ面に樹脂面がくるように重ねた
後、下記条件で溶接を行い、溶接部断面のミクロ観察で
評価した。(2) Weldability Two test materials were piled up so that the resin surface was on the mating surface, then welded under the following conditions, and evaluated by microscopic observation of the cross section of the welded part.
【００４１】溶接条件 加圧力：300kgf、 通電：３cycles、休止：２cycles、 電流：13 kA 、 速度： 2.5 mpm。 Welding conditions : Pressure: 300 kgf, energization: 3 cycles, rest: 2 cycles, current: 13 kA, speed: 2.5 mpm.
【００４２】評価基準 ◎ ：溶着良好； ○ ：微小なブローホールあるが実用上問題なし； △ ：ブローホールあり； × ：未溶着部あり。 Evaluation Criteria ⊚: Good welding; ◯: Micro blowholes, but practically no problem; △: Blowholes; X: Unwelded portion.
【００４３】(3) 成形性
劣化ガソリン耐食性の試験と同様の条件でカップ絞りし
たサンプルについて、絞り内面側の壁の塗膜密着性を、
粘着テープでの剥離状況から目視で次のように評価し
た。(3) Deterioration of moldability With respect to a sample drawn by a cup under the same conditions as the corrosion resistance test for gasoline, the adhesion of the coating film on the wall on the inner surface side of the draw was measured.
The peeling condition with the adhesive tape was visually evaluated as follows.
【００４４】評価基準 ◎ ：剥離なし； ○ ：テープでやや顔料の付着あり； △ ：テープで明らかに剥離が認められる； × ：ほぼ全面にわたって剥離が認められる。 Evaluation Criteria ⊚: No peeling; ◯: Some adhesion of pigment on the tape; Δ: Clear peeling on the tape; ×: Peeling on almost the entire surface.
【００４５】[0045]
【表１】 [Table 1]
【００４６】表１からわかるように、Ni、Al、Ni−Alか
ら選んだ顔料Ａだけを樹脂層に存在させた比較例では、
内面耐食性 (劣化ガソリン耐食性) と成形性は良好であ
るが、溶接性が不十分であり、特にNiを含有させない
と、溶接性は非常に悪かった。これに対し、顔料の合計
量は同じままで、金属顔料Ａの一部を、本発明に従って
顔料Ｂ (リン化鉄および／またはフェロシリコン) に変
更すると、良好な内面耐食性と成形性を保持したまま、
溶接性が向上し、劣化ガソリンに対する耐食性と溶接性
および成形性が高度にバランスした燃料タンク用表面処
理鋼板を得ることができた。As can be seen from Table 1, in the comparative example in which only the pigment A selected from Ni, Al and Ni-Al was present in the resin layer,
The internal corrosion resistance (degraded gasoline corrosion resistance) and the formability were good, but the weldability was insufficient, and the weldability was extremely poor unless Ni was added. On the other hand, when a part of the metal pigment A was changed to the pigment B (iron phosphide and / or ferrosilicone) according to the present invention while maintaining the same total amount of the pigment, good internal corrosion resistance and moldability were retained. As it is,
Weldability was improved, and it was possible to obtain a surface-treated steel sheet for fuel tanks in which corrosion resistance against deteriorated gasoline and weldability and formability were highly balanced.
【００４７】(実施例２)両面Zn−55％Al溶融めっき鋼板
(めっき付着量60 g/m2)の両面に、反応型クロメート処
理を、Cr付着量20 mg/m2となるように施した。数平均分
子量25,000の熱硬化性アミン変性エポキシ樹脂をベース
樹脂とする樹脂液 (溶媒：シクロヘキサノン) に、下記
顔料とシリカ (気相法で製造された乾式シリカ) を下記
割合で分散させ、得られた塗料を、上記のクロメート処
理めっき鋼板の片面に、乾燥後の樹脂層の付着量が 0.5
〜20g/m2の付着量となるようにバーコータで塗布し、20
0℃で45秒間焼き付けて、樹脂層を形成した。(Example 2) Double-sided Zn-55% Al hot dip plated steel sheet
Reactive chromate treatment was applied to both sides of (plating adhesion amount 60 g / m 2 ) so that the Cr adhesion amount was 20 mg / m 2 . The following pigments and silica (dry-phase silica produced by the vapor phase method) are dispersed in a resin solution (solvent: cyclohexanone) containing a thermosetting amine-modified epoxy resin with a number average molecular weight of 25,000 as the base resin in the following proportions: The above coating is applied to one side of the above chromate-treated plated steel sheet with 0.5% of the resin layer after drying.
Was coated with a bar coater such that the coating weight of ~20g / m 2, 20
The resin layer was formed by baking at 0 ° C. for 45 seconds.
【００４８】樹脂層組成
アミン変性エポキシ樹脂 60重量部
Ni粉 (粒径0.8 μｍ粒状) 10重量部
Al粉 (粒径13μｍ鱗片状) 12重量部
フェロシリコン (粒径４μｍ粒状) 8重量部
シリカ (粒径0.2 μｍ粒状) 10重量部
作成した表面処理鋼板の性能を実施例１と同様に評価し
た結果を、樹脂層の付着量と一緒に表２に示す。樹脂層
の付着量が３g/m2未満であると、十分な劣化ガソリン耐
食性が得られず、この付着量が10g/m2を越えると、樹脂
層が厚くなりすぎ、十分な溶接性が得られない。 Resin layer composition Amine-modified epoxy resin 60 parts by weight Ni powder (particle size 0.8 μm granular) 10 parts by weight Al powder (particle size 13 μm scaly) 12 parts by weight Ferrosilicon (particle size 4 μm granular) 8 parts by weight Silica ( 10 parts by weight of the surface-treated steel sheet prepared was evaluated in the same manner as in Example 1, and the results are shown in Table 2 together with the amount of the resin layer deposited. If the amount of resin layer adhered is less than 3 g / m 2 , sufficient deteriorated gasoline corrosion resistance cannot be obtained. If the amount of resin layer adhered exceeds 10 g / m 2 , the resin layer becomes too thick and sufficient weldability is obtained. I can't.
【００４９】[0049]
【表２】 [Table 2]
【００５０】(実施例３)両面電気Znめっき鋼板 (めっき
付着量50 g/m2)の両面に、浸漬型リン酸亜鉛処理を付着
量1.5 g/m2となるように施した。実施例２で使用したの
と同じアミン変性エポキシ樹脂をベース樹脂とし、顔料
粒径と各顔料の含有量および顔料合計量を表３に示した
ように変化させた塗料を作成した。この塗料を、乾燥後
の樹脂層の付着量が約６g/m2となるように、上記の浸漬
型リン酸亜鉛処理めっき鋼板の片面に塗布し、240 ℃で
80秒間焼き付けて、樹脂層を形成した。こうして作成し
た表面処理鋼板の性能を実施例１と同様に調べた結果を
表３に併せて示す。Example 3 Immersion type zinc phosphate treatment was applied to both surfaces of a double-sided electric Zn-plated steel sheet (coating adhesion amount 50 g / m 2 ) so that the adhesion amount was 1.5 g / m 2 . The same amine-modified epoxy resin used in Example 2 was used as a base resin, and a paint was prepared in which the pigment particle size, the content of each pigment, and the total pigment amount were changed as shown in Table 3. This paint was applied to one side of the above dipping-type zinc phosphate-treated plated steel sheet so that the amount of the resin layer deposited after drying was about 6 g / m 2, and at 240 ° C
The resin layer was formed by baking for 80 seconds. The results of examining the performance of the surface-treated steel sheet thus produced in the same manner as in Example 1 are also shown in Table 3.
【００５１】[0051]
【表３】 [Table 3]
【００５２】表３に示すように、樹脂層中の顔料の合計
量が15重量％より少なくなると、溶接性が不足し、顔料
の合計量が70重量％を超えると、樹脂層中の顔料比率が
高すぎ、成型時に顔料の脱落が生じるようになり、成形
性が不十分となる。As shown in Table 3, when the total amount of the pigments in the resin layer is less than 15% by weight, the weldability is insufficient, and when the total amount of the pigments exceeds 70% by weight, the pigment ratio in the resin layer is high. Is too high, and the pigment comes off during molding, resulting in insufficient moldability.
【００５３】(実施例４)両面Zn−10％Fe合金化溶融めっ
き鋼板 (めっき付着量45 g/m2)の両面に、浸漬型リン酸
亜鉛処理を、付着量1.5 g/m2となるように施した。実施
例２で使用したのと同じアミン変性エポキシ樹脂をベー
ス樹脂とし、顔料Ａ (Ni、Al、Ni−Al合金の中から少な
くとも１種) と顔料Ｂ (リン化鉄あるいはフェロシリコ
ンより少なくとも１種) を、顔料合計量は樹脂重量の30
重量％と一定で顔料Ａ／顔料Ｂの重量比を 100/0〜0/10
0 の間で変化させて添加した塗料を作成した。この塗料
を、乾燥後の樹脂層の付着量が約５g/m2となるように、
上記の浸漬型リン酸亜鉛処理めっき鋼板の片面に塗布
し、240 ℃で80秒間焼き付けて、樹脂層を形成した。こ
うして作成した表面処理鋼板の性能を実施例１と同様に
調べた結果を、樹脂層の組成と共に表４に示す。(Example 4) Double-sided Zn-10% Fe alloyed hot-dip galvanized steel sheet (plating adhesion amount: 45 g / m 2 ) was subjected to immersion-type zinc phosphate treatment to an adhesion amount of 1.5 g / m 2. So that The same amine-modified epoxy resin as used in Example 2 was used as a base resin, and pigment A (at least one of Ni, Al, and Ni-Al alloys) and pigment B (at least one of iron phosphide or ferrosilicon) were used. ), The total amount of pigment is 30% of the resin weight.
The weight ratio of pigment A / pigment B is 100/0 to 0/10 at a constant value of 100% by weight.
Paints were prepared by changing the value between 0 and 0. Apply this coating so that the amount of resin layer deposited after drying will be about 5 g / m 2 .
It was applied to one surface of the above-mentioned immersion type zinc phosphate-treated plated steel sheet and baked at 240 ° C. for 80 seconds to form a resin layer. The results of examining the performance of the surface-treated steel sheet thus produced in the same manner as in Example 1 are shown in Table 4 together with the composition of the resin layer.
【００５４】[0054]
【表４】 [Table 4]
【００５５】表４に示すように、顔料Ａ／顔料Ｂの重量
比が90／10を超えるようになると溶接性が低下するよう
になり、この重量比が30／70より小さくなると、内面の
劣化ガソリン耐食性が劣化するようになる。溶接性と劣
化ガソリン耐食性のバランスを考慮すると、より好まし
い顔料Ａ／顔料Ｂの重量比は80／20〜40／60の範囲であ
る。As shown in Table 4, when the pigment A / pigment B weight ratio exceeds 90/10, the weldability deteriorates. When this weight ratio is less than 30/70, the inner surface deteriorates. Gasoline corrosion resistance will deteriorate. Considering the balance between the weldability and the deteriorated gasoline corrosion resistance, the more preferable pigment A / pigment B weight ratio is in the range of 80/20 to 40/60.
【００５６】[0056]
【発明の効果】本発明により、比較的安価で大量生産さ
れているZn系めっき鋼板を素材として、劣化ガソリン耐
食性に優れ、かつ高度の溶接性を備え、成形性も良好
な、自動車の燃料タンク用に適した、燃料容器用表面処
理鋼板が提供され、ユーザーの使い勝手がよい高品質の
燃料タンクを比較的安価に供給することが可能となる。EFFECTS OF THE INVENTION According to the present invention, a Zn-plated steel sheet, which is relatively inexpensive and mass-produced, is used as a raw material and has excellent gasoline corrosion resistance, high weldability, and good formability. A surface-treated steel sheet for a fuel container suitable for use is provided, and it becomes possible to supply a high-quality fuel tank that is convenient for users and is relatively inexpensive.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０９Ｄ 5/08 Ｃ０９Ｄ 7/12 Ｚ 7/12 163/00 163/00 175/04 175/04 Ｂ６０Ｋ 15/02 Ａ (72)発明者 福井 清之 大阪市中央区北浜４丁目５番33号 住友 金属工業株式会社内 (72)発明者 引野 真也 和歌山市湊1850番地 住友金属工業株式 会社和歌山製鉄所内 (72)発明者 大芝 敏春 大阪市北区大淀北２丁目１番２号 日本 ペイント株式会社内 (56)参考文献 特開 昭61−246058（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 30/00 B05D 7/14 B05D 7/24 302 B05D 7/24 303 B60K 15/03 C09D 5/08 C09D 7/12 C09D 163/00 C09D 175/04 ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI C09D 5/08 C09D 7/12 Z 7/12 163/00 163/00 175/04 175/04 B60K 15/02 A (72) Inventor Kiyoyuki Fukui 4-53-3 Kitahama, Chuo-ku, Osaka City Sumitomo Metal Industries, Ltd. (72) Inventor Shinya Hikino 1850 Minato, Wakayama City Sumitomo Metal Industries, Ltd. (72) Inventor Oshiba Toshiharu 2-1-2 Oyodokita, Kita-ku, Osaka, Japan Paint Co., Ltd. (56) Reference JP-A-61-246058 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C23C 30/00 B05D 7/14 B05D 7/24 302 B05D 7/24 303 B60K 15/03 C09D 5/08 C09D 7/12 C09D 163/00 C09D 175/04
Claims (6)
層に、Ni、AlおよびNi−Al合金から選ばれた１種もしく
は２種以上の金属顔料Ａと、リン化鉄およびフェロシリ
コンから選ばれた１種もしくは２種の顔料Ｂとを、顔料
Ａ／顔料Ｂの重量比が90／10〜30／70の範囲、かつ顔料
合計量が樹脂層の15〜70重量％の範囲となる量で含有す
る熱硬化型樹脂層を３〜10 g/m2 の付着量で有すること
を特徴とする、燃料容器用表面処理鋼板。1. At least one surface of a zinc-based plated steel sheet is selected from one or more metal pigments A selected from Ni, Al, and Ni—Al alloys, and iron phosphide and ferrosilicon. Contains 1 or 2 kinds of pigment B in an amount such that the weight ratio of pigment A / pigment B is in the range of 90/10 to 30/70 and the total amount of the pigment is in the range of 15 to 70% by weight of the resin layer. A surface-treated steel sheet for a fuel container, characterized in that it has a thermosetting resin layer with an adhesion amount of 3 to 10 g / m 2 .
ｍの範囲である請求項１記載の燃料容器用表面処理鋼
板。2. The average particle size of each pigment is 0.5 to 15 μm.
The surface-treated steel sheet for a fuel container according to claim 1, which is in a range of m.
である請求項１または２記載の燃料容器用表面処理鋼
板。3. The surface-treated steel sheet for a fuel container according to claim 1, wherein the resin component in the resin layer is a modified epoxy resin.
Al合金から選ばれた１種もしくは２種以上の金属顔料Ａ
と、リン化鉄およびフェロシリコンから選ばれた１種も
しくは２種の顔料Ｂとを含有する塗料組成物であって、
顔料Ａ／顔料Ｂの重量比が90／10〜30／70の範囲、かつ
顔料合計量が該塗料組成物の固形分重量に対して15〜70
重量％の範囲となる量であることを特徴とする、燃料容
器用表面処理鋼板の製造用塗料組成物。4. In addition to the resin and solvent, Ni, Al and Ni-
One or more metal pigments A selected from Al alloys
And a coating composition containing one or two pigments B selected from iron phosphide and ferrosilicon,
The weight ratio of pigment A / pigment B is in the range of 90/10 to 30/70, and the total amount of the pigment is 15 to 70 relative to the solid content weight of the coating composition.
A coating composition for producing a surface-treated steel sheet for a fuel container, characterized in that the amount is in the range of% by weight.
ｍの範囲である請求項４記載の塗料組成物。5. The average particle size of each pigment is 0.5 to 15 μm.
The coating composition according to claim 4, which is in the range of m.
である請求項４または５記載の塗料組成物。6. The coating composition according to claim 4, wherein the resin component in the resin layer is a modified epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12740999A JP3389884B2 (en) | 1999-05-07 | 1999-05-07 | Surface treated steel sheet for fuel container and paint composition therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12740999A JP3389884B2 (en) | 1999-05-07 | 1999-05-07 | Surface treated steel sheet for fuel container and paint composition therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000319790A JP2000319790A (en) | 2000-11-21 |
| JP3389884B2 true JP3389884B2 (en) | 2003-03-24 |
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ID=14959271
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|---|---|---|---|
| JP12740999A Expired - Fee Related JP3389884B2 (en) | 1999-05-07 | 1999-05-07 | Surface treated steel sheet for fuel container and paint composition therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002254555A (en) * | 2001-03-01 | 2002-09-11 | Nippon Steel Corp | Metallic material with treated surface showing superb corrosion resistance |
| CN1668460B (en) | 2002-05-14 | 2010-05-26 | 新日本制铁株式会社 | Weldable coated metal material with superior corrosion resistance for formed part |
| JP2005015834A (en) * | 2003-06-25 | 2005-01-20 | Nippon Steel Corp | Highly corrosion-resistant coated steel sheet capable of being welded superior in corrosion resistance |
| JP5217309B2 (en) * | 2007-09-10 | 2013-06-19 | パナソニック株式会社 | Fin and tube heat exchanger |
| JP5056739B2 (en) * | 2008-12-10 | 2012-10-24 | パナソニック株式会社 | Aluminum tube connection structure, connection method and heat exchanger |
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| JP2000319790A (en) | 2000-11-21 |
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