JP3307321B2 - Coated steel with excellent weather resistance - Google Patents
Coated steel with excellent weather resistanceInfo
- Publication number
- JP3307321B2 JP3307321B2 JP08426698A JP8426698A JP3307321B2 JP 3307321 B2 JP3307321 B2 JP 3307321B2 JP 08426698 A JP08426698 A JP 08426698A JP 8426698 A JP8426698 A JP 8426698A JP 3307321 B2 JP3307321 B2 JP 3307321B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- rust
- chromium
- steel material
- sodium sulfate
- 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 - Lifetime
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)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (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、クロム溶出量の少
ない耐候性に優れた被覆鋼材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated steel material having a low chromium elution amount and excellent weather resistance.
【０００２】[0002]
【従来の技術】一般に鋼にＰ、Ｃｕ、Ｃｒ、Ｎｉ等の元
素を添加することにより、大気中における耐食性を向上
させることができる。これらの低合金鋼は耐候性鋼と呼
ばれるが、屋外において数年で腐食に対して保護性のあ
る錆（以下、耐候性安定錆という）を形成し、以後塗装
等の耐食処理作業を不要とするいわゆるメインテナンス
フリー鋼である。2. Description of the Related Art In general, corrosion resistance in the atmosphere can be improved by adding elements such as P, Cu, Cr, and Ni to steel. These low-alloy steels are called weather-resistant steels, but they form rust that protects against corrosion in a few years outdoors (hereinafter referred to as weather-resistant stable rust), which eliminates the need for corrosion-resistant work such as painting. It is a so-called maintenance-free steel.
【０００３】しかしながら、耐候性安定錆が形成される
までに数年かかるため、それまでの期間中に赤錆や黄錆
等の浮き錆や流れ錆を生じ、外見的に好ましくないばか
りでなく周囲環境の汚染原因にもなるという問題を残し
ている。特に海塩粒子が飛来する環境においては、この
傾向が著しく問題であった。However, since it takes several years for stable rust to be formed, floating rust and flowing rust such as red rust and yellow rust occur during the period, which is not only unfavorable in appearance but also affects the surrounding environment. The problem remains that it can cause pollution. This tendency is a serious problem especially in an environment where sea salt particles fly.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、先に、
特開平０６−２２６１９８号公報に、硫酸クロムを適当
量含有する有機樹脂を鋼材表面あるいは鋼材の錆層に被
覆することにより、早期に耐候性安定錆層を形成できる
ことを開示している。SUMMARY OF THE INVENTION The present inventors have previously described
Japanese Patent Application Laid-Open No. 06-226198 discloses that a weatherable stable rust layer can be formed at an early stage by coating an organic resin containing an appropriate amount of chromium sulfate on a steel material surface or a rust layer of the steel material.
【０００５】しかし、硫酸クロムを使用しているため、
クロムイオンの溶出の問題があり、クロムイオンの溶出
を抑制しながら早期に耐候性安定錆層を形成できるいわ
ゆる環境に優しい鋼材が求められていた。However, since chromium sulfate is used,
There is a problem of elution of chromium ions, and a so-called environmentally friendly steel material capable of forming a weather-resistant stable rust layer early while suppressing elution of chromium ions has been demanded.
【０００６】本発明の目的は、硫酸クロムを添加した有
機樹脂被覆鋼材並みの耐候性安定錆層を形成でき、しか
も、クロムイオンの溶出の問題の少ない耐候性に優れた
被覆鋼材を提供することにある。An object of the present invention is to provide a coated steel material which can form a stable rust layer having the same weather resistance as an organic resin coated steel material to which chromium sulfate has been added and which has little problem of elution of chromium ions and has excellent weather resistance. It is in.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、試験を重
ね以下の(A) 〜(E) の知見を得た。 (A) 硫酸クロムに、硫酸ナトリウムを加えた水溶液を含
有させた有機樹脂で、鋼材表面あるいは鋼材の錆層の上
を被覆すると、クロムイオンの溶出量は、硫酸ナトリウ
ムの混合モル比（硫酸ナトリウム／（硫酸クロム＋硫酸
ナトリウム））が高いほど低下する。Means for Solving the Problems The present inventors have conducted tests and obtained the following findings (A) to (E). (A) When the surface of a steel material or the rust layer of a steel material is coated with an organic resin containing an aqueous solution obtained by adding sodium sulfate to chromium sulfate, the elution amount of chromium ions is determined by the molar ratio of sodium sulfate (sodium sulfate). / (Chromium sulfate + sodium sulfate)) decreases.
【０００８】(B) 上記のクロムイオン溶出量の抑制は、
早期に耐候性安定錆層を形成できる特性を維持したまま
可能である。 (C) 硫酸ナトリウムの水に対する常温での溶解度は、硫
酸クロムの１．５〜２倍と高く、耐候性安定錆層の形成
に有効な硫酸イオンを大量に保持できる。(B) The suppression of the elution amount of chromium ions described above
It is possible to maintain the property of forming a weatherable stable rust layer early. (C) The solubility of sodium sulfate in water at room temperature is 1.5 to 2 times as high as that of chromium sulfate, and a large amount of sulfate ions effective for forming a weather-resistant stable rust layer can be retained.
【０００９】(D) クロムイオンは、錆の結晶粒を微細化
し、錆を緻密化する作用があるが極少量あればよく、大
半の量を硫酸ナトリウムに代替できる。 (E) 硫酸クロムに、硫酸ナトリウムを加えた水溶液を含
有させた有機樹脂で、鋼材表面あるいは鋼材の錆層の上
に被覆してもよいし、水溶液を直接鋼材表面に塗り、乾
燥させることにより付着させてもよく、有機樹脂を媒体
にしなくても同様の効果が得られる。(D) Chromium ions have the effect of refining rust crystal grains and densifying rust, but only a very small amount is required, and most of the amount can be replaced by sodium sulfate. (E) An organic resin containing an aqueous solution obtained by adding sodium sulfate to chromium sulfate may be coated on the steel surface or on the rust layer of the steel material, or the aqueous solution may be directly applied to the steel surface and dried. The same effect may be obtained without using an organic resin as a medium.
【００１０】本発明は、以上の知見に基づいてなされた
もので、その要旨は、下記(1) 〜(3) の通りである。 (1) 鋼材の表面または該表面に形成された錆層の上に順
次設けられた下層および上層の各被覆層を備えた鋼材で
あって、前記下層が、付着量が０．１〜３０mg/cm2の硫
酸クロムおよび硫酸ナトリウムの混合物の層から構成さ
れ、かつ前記上層が、厚さ５〜７５μm の有機樹脂層で
あることを特徴とする耐候性に優れた被覆鋼材。The present invention has been made based on the above findings, and the gist is as follows (1) to (3). (1) A steel material comprising a lower layer and an upper coating layer sequentially provided on a surface of a steel material or a rust layer formed on the surface, wherein the lower layer has an adhesion amount of 0.1 to 30 mg / it is composed of a layer of a mixture of chromium sulphate and sodium sulphate in cm 2, and coated steel the upper layer, excellent in weather resistance, characterized in that an organic resin layer having a thickness of 5～75Myuemu.
【００１１】(2) 鋼材の表面または該表面に形成された
錆層の上に順次設けられた下層および上層の各被覆層を
備えた鋼材であって、前記下層が、厚み１〜７５μm
の、硫酸クロムおよび硫酸ナトリウムを合計で０．１〜
１５重量％含有する有機樹脂層から構成され、かつ前記
上層が、厚さ５〜７５μm の有機樹脂層であることを特
徴とする耐候性に優れた被覆鋼材。(2) A steel material comprising a lower layer and an upper coating layer sequentially provided on a surface of the steel material or a rust layer formed on the surface, wherein the lower layer has a thickness of 1 to 75 μm.
Of chromium sulfate and sodium sulfate in total of 0.1 to
A coated steel material having excellent weather resistance, comprising an organic resin layer containing 15% by weight, wherein the upper layer is an organic resin layer having a thickness of 5 to 75 μm.
【００１２】(3) 前記下層における硫酸ナトリウムの重
量比、硫酸ナトリウム／（硫酸クロム＋硫酸ナトリウ
ム）が０．０５０〜０．９９５である、請求項１または
２に記載の耐候性に優れた被覆鋼材。(3) The coating excellent in weather resistance according to claim 1 or 2, wherein the weight ratio of sodium sulfate, sodium sulfate / (chromium sulfate + sodium sulfate) in the lower layer is 0.050 to 0.995. Steel.
【００１３】[0013]
【発明の実施の形態】本発明で使用する硫酸クロムや硫
酸ナトリムは、工業用の通常利用されているものでよ
い。BEST MODE FOR CARRYING OUT THE INVENTION The chromium sulfate and sodium sulfate used in the present invention may be those commonly used in industry.
【００１４】請求項１に記載する発明は、下層が硫酸ク
ロムおよび硫酸ナトリウムの混合物の層で構成され、該
混合物の付着量が０．１〜３０mg/cm2であり、該混合物
の層の上層として５〜７５μm の厚みの有機樹脂層で構
成されていることを特徴とする耐候性に優れた被覆鋼材
であるが、下層の混合物の付着量および上層の有機樹脂
層の厚みの限定理由について述べる。The invention according to claim 1 is characterized in that the lower layer is composed of a layer of a mixture of chromium sulfate and sodium sulfate, the amount of the mixture is 0.1 to 30 mg / cm 2 , and the upper layer of the mixture is It is a coated steel excellent in weather resistance characterized in that it is composed of an organic resin layer having a thickness of 5 to 75 μm, but the reason for limiting the adhesion amount of the lower layer mixture and the thickness of the upper organic resin layer will be described. .
【００１５】下層の混合物の付着量は、０．１mg/cm2未
満では、硫酸イオンが不足し、良好な耐候性安定錆層が
得られず、３０mg/cm2を超えると剥離し易くなり、０．
１〜３０mg/cm2がよい。好ましくは、５〜２０mg/cm2で
ある。[0015] If the amount of the mixture of the lower layer is less than 0.1 mg / cm 2 , sulfate ions are insufficient, and a good weather-resistant and stable rust layer cannot be obtained. If the amount exceeds 30 mg / cm 2 , the mixture tends to peel off. 0.
1-30 mg / cm 2 is good. Preferably, it is 5 to 20 mg / cm 2 .
【００１６】上層の有機樹脂層の厚みは、５μm 未満の
薄い膜厚では、いわゆるバリア効果が低く、下地鋼材の
腐食で生成されてくる鉄イオンのしみ出しを完全に防ぐ
ことができず流れ錆を生じ、海塩粒子が飛来する悪環境
においては、塩素イオンの透過により過度の腐食を生
じ、耐候性安定錆の生成が阻害される。上層の有機樹脂
層の厚みが７５μm を越えると、バリア−効果が高くな
り過ぎ、下地鋼面に耐候性安定錆を形成するのに長時間
を要するようになり、早期に耐候性安定錆の生成ができ
なくなる。以上の理由から、上層の有機樹脂層の厚み
は、５〜７５μm がよい。好ましくは、２０〜７５μm
である。If the thickness of the upper organic resin layer is less than 5 μm, the so-called barrier effect is low, and the exudation of iron ions generated by the corrosion of the base steel cannot be completely prevented. In a bad environment in which sea salt particles fly, excessive corrosion occurs due to permeation of chloride ions, and the formation of weather-resistant stable rust is hindered. If the thickness of the upper organic resin layer exceeds 75 μm, the barrier effect becomes too high, and it takes a long time to form the weather-resistant stable rust on the base steel surface, and the weather-resistant stable rust is formed early. Can not be done. For the above reasons, the thickness of the upper organic resin layer is preferably 5 to 75 μm. Preferably, 20 to 75 μm
It is.
【００１７】請求項２に記載する発明は、鋼材表面ある
いは鋼材の錆層の上に、上下層から構成される被覆鋼材
において、下層が硫酸クロムおよび硫酸ナトリウムを
０．１〜１５重量％含有する有機樹脂層で構成され、該
有機樹脂層の厚みが１〜７５μm である層の上に、上層
として５〜７５μm の厚みの有機樹脂層で構成されてい
ることを特徴とする耐候性に優れた被覆鋼材であるが、
下層の硫酸クロムおよび硫酸ナトリウム含有濃度、有機
樹脂層の厚み、および上層の有機樹脂層厚みの限定理由
について述べる。According to a second aspect of the present invention, in a coated steel material composed of upper and lower layers on the surface of a steel material or on a rust layer of the steel material, the lower layer contains 0.1 to 15% by weight of chromium sulfate and sodium sulfate. Excellent weather resistance characterized in that the organic resin layer is formed of an organic resin layer having a thickness of 5 to 75 μm as an upper layer on a layer having a thickness of 1 to 75 μm. It is coated steel,
The reasons for limiting the concentration of chromium sulfate and sodium sulfate in the lower layer, the thickness of the organic resin layer, and the thickness of the upper organic resin layer will be described.
【００１８】下層における硫酸クロムおよび硫酸ナトリ
ウムの合計の含有濃度は、０．１％未満では、硫酸イオ
ンが不足し、良好な耐候性安定錆層が得られず、１５％
を超えると、これら無機物質と結合する役割を持つ有機
樹脂分が不足するため、被膜が脆くなるとともに被膜表
面から鋼面に達するひび割れ等が形成されて、流れ錆を
生じることが懸念される。以上から、下層における硫酸
クロムおよび硫酸ナトリウムの合計の含有濃度は、０．
１〜１５重量％がよい。好ましくは、２〜１２重量％で
ある。If the total concentration of chromium sulfate and sodium sulfate in the lower layer is less than 0.1%, sulfate ions are insufficient, and a good weatherable stable rust layer cannot be obtained.
If it exceeds 300, there is a shortage of the organic resin which plays a role of binding to these inorganic substances, so that the coating becomes brittle and cracks reaching the steel surface from the coating surface are formed, which may cause flow rust. From the above, the total content concentration of chromium sulfate and sodium sulfate in the lower layer is 0.1%.
1-15% by weight is preferred. Preferably, it is 2 to 12% by weight.
【００１９】なお、有機樹脂中の硫酸クロムおよび硫酸
ナトリウムの濃度は、乾燥固化した後の濃度を示す。被
覆前には、適当量の溶剤または水により塗装作業に適し
た粘度に調整されていることは言うまでもないことであ
り、溶剤または水分は、塗装後自然乾燥により蒸散す
る。The concentrations of chromium sulfate and sodium sulfate in the organic resin indicate the concentrations after drying and solidification. It is needless to say that the viscosity is adjusted to a level suitable for the coating operation with an appropriate amount of a solvent or water before coating, and the solvent or water evaporates by natural drying after coating.
【００２０】下層の有機樹脂層の厚みは、１μm 未満の
薄い膜厚では、十分な硫酸クロムや硫酸ナトリウムを保
持できず、７５μm を超えると下記の上層の膜厚を考慮
すると過剰の膜厚になる。以上から、下層の有機樹脂層
の厚みは、１〜７５μm がよい。好ましくは、２０〜７
５μm である。If the thickness of the lower organic resin layer is less than 1 μm, sufficient chromium sulfate and sodium sulfate cannot be maintained, and if it exceeds 75 μm, the thickness of the upper layer becomes excessive considering the thickness of the following upper layer. Become. From the above, the thickness of the lower organic resin layer is preferably 1 to 75 μm. Preferably, 20 to 7
5 μm.
【００２１】上層の有機樹脂層の厚みは、５μm 未満の
薄い膜厚では、バリア効果が低く、下地鋼材の腐食で生
成されてくる鉄イオンのしみ出しを防ぐことができず流
れ錆を生じ、海塩粒子の飛来する悪環境において、過度
の水分や塩素イオンの透過により過度に腐食を生じ、連
続した耐候性安定錆被膜の生成が阻害され、硫酸イオン
の溶出やクロムイオンの溶出を抑制する効果が小さくな
る。上層の有機樹脂層の厚みが７５μm を超えると、バ
リア効果が高くなりすぎて下地鋼面に耐候性安定錆を形
成するのに長時間を要するようになる。以上から、上層
の有機樹脂層の厚みは、５〜７５μm がよい。好ましく
は、２５〜７５μm である。If the thickness of the upper organic resin layer is less than 5 μm, the barrier effect is low and iron ions generated by corrosion of the base steel cannot be prevented from leaking out, resulting in flow rust. In a bad environment where sea salt particles fly, excessive corrosion occurs due to excessive moisture and chloride ion permeation, which inhibits the formation of a continuous weather-resistant stable rust film and suppresses the elution of sulfate ions and chromium ions The effect is reduced. If the thickness of the upper organic resin layer exceeds 75 μm, the barrier effect becomes too high and it takes a long time to form weather-resistant stable rust on the base steel surface. From the above, the thickness of the upper organic resin layer is preferably 5 to 75 μm. Preferably, it is 25 to 75 μm.
【００２２】請求項３に記載する発明は、硫酸ナトリウ
ムの重量比、硫酸ナトリウム／（硫酸クロム＋硫酸ナト
リウム）が０．０５０〜０．９９５であることを特徴と
するものであるが、好ましくは、０．２〜０．８であ
る。The invention according to claim 3 is characterized in that the weight ratio of sodium sulfate, that is, sodium sulfate / (chromium sulfate + sodium sulfate) is 0.050 to 0.995. , 0.2 to 0.8.
【００２３】その理由は、硫酸クロムは生成した錆を緻
密化させ防食性を向上させる作用があり、ある程度必要
であるが、硫酸ナトリウムは水に対する溶解度が大き
く、錆を早く生成させる硫酸イオンを多く保有できる作
用があり、両方の作用を考慮すると上記範囲が好まし
く、０．０５０〜０．９９５の範囲であればよい。The reason is that chromium sulfate has the effect of densifying the formed rust and improving the anticorrosion property, and is required to some extent. However, sodium sulfate has a high solubility in water and has a large amount of sulfate ions to form rust quickly. There is an action that can be retained, and the above range is preferable in consideration of both actions, and it may be in the range of 0.050 to 0.995.
【００２４】本発明の有機樹脂層の被覆の機能は、適度
の水分や酸素を鋼面に供給することにより、硫酸化合物
やクロムの溶出を減らし、耐候性安定錆を生成させる働
きを持つものである。The function of the coating of the organic resin layer of the present invention is to supply a suitable amount of moisture or oxygen to the steel surface, thereby reducing the elution of a sulfuric acid compound or chromium and generating weather-resistant stable rust. is there.
【００２５】本発明に使用される有機樹脂は特に制限を
受けるものではなく、エポキシ樹脂、ウレタン樹脂、ビ
ニル樹脂、ポリエステル樹脂、アクリル樹脂、アルキド
樹脂、ブチラ−ル樹脂、フタル酸樹脂等を例示すること
ができる。また上記樹脂を塗料化して塗装を行うが、溶
剤系の塗料にしても、水性塗料にしても特に問題ない。The organic resin used in the present invention is not particularly limited, and examples thereof include an epoxy resin, a urethane resin, a vinyl resin, a polyester resin, an acrylic resin, an alkyd resin, a butyral resin, and a phthalic acid resin. be able to. In addition, the above resin is converted into a paint and the coating is carried out. However, there is no particular problem whether it is a solvent-based paint or an aqueous paint.
【００２６】なお、本発明に用いられる鋼材は、特に鋼
種を限定されるものではなく普通鋼であっても、耐候性
鋼であっても構わない。すなわち、本発明の樹脂被覆中
の硫酸クロム或いは硫酸ナトリウムの作用により、普通
鋼であってもその錆は最終的に化学的に安定で緻密な耐
候性安定錆に変態し、保護作用を発揮できる。The steel used in the present invention is not particularly limited in steel type, and may be ordinary steel or weather-resistant steel. That is, by the action of chromium sulfate or sodium sulfate in the resin coating of the present invention, even for ordinary steel, the rust is finally transformed into chemically stable and dense weather-resistant stable rust, which can exert a protective effect. .
【００２７】ただし、生成された保護性の錆層に何らか
の外力が作用して亀裂の生成や剥離を生じたとき、普通
鋼は、その損傷部において再度耐候性安定錆を生成する
自己修復性能に劣るため、耐候性鋼を用いることが好ま
しい。However, when any external force acts on the generated protective rust layer to cause cracking or peeling, ordinary steel has a self-healing performance that generates weatherable stable rust again at the damaged portion. It is preferable to use weather-resistant steel because it is inferior.
【００２８】[0028]
【実施例】表１に、本発明の実施例に用いた試験片の化
学成分の濃度（重量％）を示す。EXAMPLES Table 1 shows the concentrations (% by weight) of the chemical components of the test pieces used in the examples of the present invention.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表２に、試験片の前処理方法に示す。試験
片の寸法は１５０×７０×３．２（mm）であり、処理前
の表面はエメリ紙研磨およびバフ研磨により、鏡面加工
したものを使用した。Table 2 shows the pretreatment methods for the test pieces. The dimensions of the test piece were 150 × 70 × 3.2 (mm), and the surface before the treatment was mirror-finished by emery paper polishing and buff polishing.
【００３１】[0031]
【表２】 [Table 2]
【００３２】表３に、被覆材に用いた基材樹脂組成を示
す。Table 3 shows the base resin composition used for the coating material.
【００３３】[0033]
【表３】 [Table 3]
【００３４】硫酸クロムと硫酸ナトリウムの混合物の付
着量（mg/cm2）の調整は、０．１〜４５．０重量％の硫
酸クロムと硫酸ナトリウムの混合水溶液を水膜４００μ
m をスプレ方法で塗布し、乾燥させることを繰り返すこ
とにより行った。The amount of the mixture (mg / cm 2 ) of the mixture of chromium sulfate and sodium sulfate was adjusted by using a mixed aqueous solution of 0.1 to 45.0% by weight of chromium sulfate and sodium sulfate with a water film of 400 μm.
m was applied by a spray method and dried repeatedly.
【００３５】有機樹脂の塗布は、適当量の溶剤を加えて
粘度を２００〜１０００CPS にした塗料を作り、エアー
スプレ塗装の方法で行った。表４は実施例１を、表５は
実施例２をそれぞれ示す。The application of the organic resin was performed by an air spray coating method by preparing a coating material having a viscosity of 200 to 1000 CPS by adding an appropriate amount of a solvent. Table 4 shows Example 1 and Table 5 shows Example 2.
【００３６】表４および５に示す条件にて、試験片を作
成し、海岸より１０m の位置にある工業地帯に１年間暴
露し、耐候性安定錆率（％) 求めた。耐候性安定錆率
（％)は、暴露後の試験片について偏光顕微鏡による断
面観察により耐候性安定錆の生成有無を調べ、画像解析
処理により全錆中に対する耐候性安定錆量を百分率で求
めたが、目標の耐候性安定錆の生成比率を５０％以上と
した。Test pieces were prepared under the conditions shown in Tables 4 and 5, and were exposed to an industrial zone 10 m from the coast for one year to determine the weather resistance and stable rust ratio (%). The weathering-stable rust ratio (%) was determined by examining the presence or absence of weathering-stable rust by observing a cross section of a test piece after exposure with a polarizing microscope, and determining the amount of weathering-stable rust in the total rust in percentage by image analysis. However, the target weather resistant stable rust generation ratio was set to 50% or more.
【００３７】[0037]
【表４】 [Table 4]
【００３８】[0038]
【表５】 [Table 5]
【００３９】また、表４および５に示すクロム溶出量比
の評価は、下記の手順で行った。 １．試験片をイオン交換水３００mlを入れたビーカーに
１分間浸漬後、試験片を引き上げ、別のビーカーに同様
に浸漬する。 ２．各１分毎に５回繰り返す。 ３．６回目以降は、５分間隔で５回繰り返す。 ４．上記で溶出した全クロム量を原子吸光で調べた。 ５．対象試験片が硫酸クロムを全量であるとした時の溶
出量を１００％として、溶出量を相対比較する。すなわ
ち、下記式から求めることができる。 溶出量（％）＝Ｘ％の（硫酸クロム＋硫酸ナトリウム）
混合材のクロム溶出量／（Ｘ％の硫酸クロム単独材のク
ロム溶出量）×１００。The chromium elution ratios shown in Tables 4 and 5 were evaluated according to the following procedure. 1. After immersing the test piece in a beaker containing 300 ml of ion-exchanged water for 1 minute, the test piece is pulled up and immersed in another beaker in the same manner. 2. Repeat 5 times each minute. 3. After the sixth time, repeat 5 times at 5 minute intervals. 4. The total amount of chromium eluted above was examined by atomic absorption. 5. The relative elution amount is set as 100% of the elution amount when the target test piece is assumed to be chromium sulfate as the total amount. That is, it can be obtained from the following equation. Elution amount (%) = X% (chromium sulfate + sodium sulfate)
The amount of chromium eluted from the mixed material / (the amount of chromium eluted from X% chromium sulfate alone) × 100.
【００４０】（実施例１）表４に示す試験番号１〜９の
本発明例は、耐候性安定錆率が６６％以上あり、クロム
溶出量も５％以下に抑えられた。一方、比較例１０〜１
４に示すように、上層被覆をしていないか、被覆厚が５
μm 未満および７５μm を超えると、耐候性安定錆率が
５０％未満となった。(Example 1) In the examples of the present invention of Test Nos. 1 to 9 shown in Table 4, the rust rate of weathering stability was 66% or more, and the elution amount of chromium was suppressed to 5% or less. On the other hand, Comparative Examples 10 to 1
As shown in FIG. 4, the upper layer is not coated or the coating thickness is 5
If it is less than μm or more than 75 μm, the weather resistance stable rust ratio was less than 50%.
【００４１】また、硫酸クロムおよび硫酸ナトリウムの
合計量が０．１mg/cm2未満および３０mg/cm2を超える
と、耐候性安定錆率が５０％未満となった。Further, when the total amount of chromium sulphate and sodium sulphate is more than 0.1 mg / cm 2 and less than 30 mg / cm 2, weathering stability rust ratio was less than 50%.
【００４２】（実施例２）表５に示す試験番号１５〜２
０の本発明例は、耐候性安定錆率が５３％以上あり、ク
ロム溶出量も２１％以下に抑えられた。一方、比較例２
１〜２３に示すように、上層被覆をしていないか、被覆
厚が５μm 未満および７５μm を超えると耐候性安定錆
率が５０％未満となった。(Example 2) Test numbers 15 to 2 shown in Table 5
In the example of the present invention of 0, the weather resistance stable rust ratio was 53% or more, and the chromium elution amount was suppressed to 21% or less. On the other hand, Comparative Example 2
As shown in Nos. 1 to 23, when the upper layer was not coated, or when the coating thickness was less than 5 μm or more than 75 μm, the weathering stability rust ratio was less than 50%.
【００４３】また、下層中の硫酸クロムおよび硫酸ナト
リウムの合計濃度が０．１％未満および１５％を超える
と、比較例２４〜２５に示すように、耐候性安定錆率が
５０％未満となった。When the total concentration of chromium sulfate and sodium sulfate in the lower layer is less than 0.1% and more than 15%, as shown in Comparative Examples 24 to 25, the weathering stable rust ratio becomes less than 50%. Was.
【００４４】さらに、下層の有機樹脂の厚みが１μm 未
満および７５μm を超えると比較例２６〜２７に示すよ
うに、耐候性安定錆率が５０％未満となった。Further, when the thickness of the lower organic resin was less than 1 μm and more than 75 μm, as shown in Comparative Examples 26 to 27, the weather resistance stable rust ratio was less than 50%.
【００４５】[0045]
【発明の効果】本発明によれば、硫酸クロムを添加した
有機樹脂被覆鋼材並みの耐候性安定錆層を形成でき、し
かも、クロムイオンの溶出量の少ない耐候性に優れた被
覆鋼材を提供できる。According to the present invention, it is possible to form a weather-resistant and stable rust layer comparable to that of an organic resin-coated steel material to which chromium sulfate is added, and to provide a coated steel material having a small amount of chromium ions eluted and having excellent weather resistance. .
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B05D 7/14 B32B 15/08 C23C 28/00 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) B05D 7/14 B32B 15/08 C23C 28/00
Claims (3)
層の上に順次設けられた下層および上層の各被覆層を備
えた鋼材であって、前記下層が、付着量が０．１〜３０
mg/cm2の硫酸クロムおよび硫酸ナトリウムの混合物の層
から構成され、かつ前記上層が、厚さ５〜７５μm の有
機樹脂層であることを特徴とする耐候性に優れた被覆鋼
材。1. A steel material comprising a lower layer and an upper coating layer sequentially provided on a surface of a steel material or a rust layer formed on the surface, wherein the lower layer has an adhesion amount of 0.1 to 0.1%. 30
A coated steel material having excellent weather resistance, comprising a layer of a mixture of chromium sulfate and sodium sulfate at a concentration of mg / cm 2 , wherein the upper layer is an organic resin layer having a thickness of 5 to 75 μm.
層の上に順次設けられた下層および上層の各被覆層を備
えた鋼材であって、前記下層が、厚み１〜７５μm の、
硫酸クロムおよび硫酸ナトリウムを合計で０．１〜１５
重量％含有する有機樹脂層から構成され、かつ前記上層
が、厚さ５〜７５μm の有機樹脂層であることを特徴と
する耐候性に優れた被覆鋼材。2. A steel material comprising a lower layer and an upper coating layer sequentially provided on a surface of a steel material or a rust layer formed on the surface, wherein the lower layer has a thickness of 1 to 75 μm.
Chromium sulfate and sodium sulfate in total of 0.1 to 15
A coated steel material having excellent weather resistance, wherein the coated steel material is constituted by an organic resin layer containing 5% by weight, and the upper layer is an organic resin layer having a thickness of 5 to 75 μm.
比、硫酸ナトリウム／（硫酸クロム＋硫酸ナトリウム）
が０．０５０〜０．９９５である、請求項１または２に
記載の耐候性に優れた被覆鋼材。3. The weight ratio of sodium sulfate in the lower layer, sodium sulfate / (chromium sulfate + sodium sulfate)
The coated steel material excellent in weather resistance according to claim 1 or 2, wherein is 0.050 to 0.995.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08426698A JP3307321B2 (en) | 1998-03-30 | 1998-03-30 | Coated steel with excellent weather resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08426698A JP3307321B2 (en) | 1998-03-30 | 1998-03-30 | Coated steel with excellent weather resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11276988A JPH11276988A (en) | 1999-10-12 |
| JP3307321B2 true JP3307321B2 (en) | 2002-07-24 |
Family
ID=13825661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08426698A Expired - Lifetime JP3307321B2 (en) | 1998-03-30 | 1998-03-30 | Coated steel with excellent weather resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3307321B2 (en) |
-
1998
- 1998-03-30 JP JP08426698A patent/JP3307321B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11276988A (en) | 1999-10-12 |
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