JPH04341579A - Vapor-deposited al-ti plated steel sheet excellent in corrosion resistance after coating - Google Patents
Vapor-deposited al-ti plated steel sheet excellent in corrosion resistance after coatingInfo
- Publication number
- JPH04341579A JPH04341579A JP14240191A JP14240191A JPH04341579A JP H04341579 A JPH04341579 A JP H04341579A JP 14240191 A JP14240191 A JP 14240191A JP 14240191 A JP14240191 A JP 14240191A JP H04341579 A JPH04341579 A JP H04341579A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- deposited
- vapor
- steel sheet
- coating
- 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.)
- Withdrawn
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 29
- 238000005260 corrosion Methods 0.000 title claims abstract description 29
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 21
- 239000010959 steel Substances 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title abstract description 13
- 239000011248 coating agent Substances 0.000 title abstract description 12
- 229910018575 Al—Ti Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 238000007747 plating Methods 0.000 claims description 30
- 238000010422 painting Methods 0.000 claims description 14
- 238000005246 galvanizing Methods 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は自動車や家電製品等に用
いられる高耐食性表面処理鋼板に関するものであり、詳
細には塗装後耐食性を向上させた蒸着Al−Tiめっき
鋼板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to highly corrosion-resistant surface-treated steel sheets used in automobiles, home appliances, etc., and more particularly to vapor-deposited Al--Ti plated steel sheets with improved corrosion resistance after painting.
【0002】0002
【従来の技術】自動車、家電、建材など耐食性を必要と
される分野においては、従来からZn−Ni、Zn−F
e、Zn−Alめっき鋼板等などのZn系合金めっき鋼
板が汎用されてきた。しかしながら近年では塩害や酸性
雨などによる使用環境の悪化にともない、より一層の耐
食性向上の要求が強い。[Prior Art] In fields where corrosion resistance is required, such as automobiles, home appliances, and building materials, Zn-Ni and Zn-F have traditionally been used.
Zn-based alloy plated steel sheets such as Zn-Al plated steel sheets and the like have been widely used. However, in recent years, as the usage environment has deteriorated due to salt damage and acid rain, there has been a strong demand for further improvement in corrosion resistance.
【0003】この要求に対し、現状では付着量の増加等
によって対応しているが、付着量を増加させることは成
形加工時にめっき層が粉末状に剥離するパウダリング現
象の発生や、スポット溶接性の低下等他の特性を損なう
危険性があり、低付着量で高耐食性の表面処理鋼板が望
まれている。[0003]Currently, this demand has been met by increasing the amount of adhesion, but increasing the amount of adhesion may cause the occurrence of powdering phenomenon in which the plating layer peels off into powder during molding, or may reduce spot weldability. There is a risk of damaging other properties such as a decrease in corrosion, so a surface-treated steel sheet with a low adhesion amount and high corrosion resistance is desired.
【0004】本発明者らは、Znよりも耐食性に優れた
金属としてAlに着目し、真空蒸着法による高耐食性A
lめっきについて詳細な検討を行った結果、蒸着Al−
Tiめっきが優れた耐食性を有することを見い出し、先
に出願した。さらに本発明者らはZn系めっき鋼板の代
替品として上記蒸着Al−Tiめっきが施された鋼板を
自動車や家電製品等に用いるパネル材へ適用することを
検討した。[0004] The present inventors focused on Al as a metal with better corrosion resistance than Zn, and developed high corrosion resistance A using a vacuum evaporation method.
As a result of detailed study on Al plating, we found that evaporated Al-
We discovered that Ti plating has excellent corrosion resistance and filed an application earlier. Furthermore, the present inventors have studied the application of the above-mentioned vapor-deposited Al-Ti plated steel sheet to panel materials used in automobiles, home appliances, etc. as a substitute for Zn-based plated steel sheet.
【0005】これらの部材は通常塗装が施されて使用さ
れるものであり、蒸着Al−Tiめっき鋼板は塗装後の
耐食性が不十分であることが判明した。これは塗装の前
処理であるりん酸塩皮膜がAlの表面に形成しにくく、
めっき層と塗膜との十分な密着性が得られないことに起
因している。[0005] These members are usually used after being painted, and it has been found that vapor-deposited Al--Ti plated steel sheets have insufficient corrosion resistance after painting. This is because a phosphate film, which is a pretreatment for painting, is difficult to form on the Al surface.
This is due to insufficient adhesion between the plating layer and the coating film.
【0006】[0006]
【発明が解決しようとする課題】本発明は上記事情に着
目してなされたものであって、他の特性を損なうことな
く優れた耐食性を有し、特に塗装後耐食性を有する蒸着
Al−Tiめっき鋼板を提供しようとするものである。[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and provides a vapor-deposited Al-Ti plating that has excellent corrosion resistance without impairing other properties, and in particular has corrosion resistance after painting. The aim is to provide steel plates.
【0007】[0007]
【課題を解決するための手段】上記目的を達成した本発
明とは、鋼板表面にTiを1〜20%含有する蒸着Al
−Ti合金めっき層が1g/m2以上形成され、その上
層にAl水酸化物および/またはAl酸化物を1〜20
%含有するZn系めっきが0.1 〜3g/m2形成さ
れてなることを要旨とするものである。[Means for Solving the Problems] The present invention, which achieves the above object, consists of depositing Al containing 1 to 20% Ti on the surface of a steel plate.
- A Ti alloy plating layer of 1 g/m2 or more is formed, and the upper layer is coated with 1 to 20 g/m of Al hydroxide and/or Al oxide.
The gist is that Zn-based plating containing 0.1 to 3 g/m2 is formed.
【0008】[0008]
【作用】本発明者らは蒸着Al−Tiめっき鋼板の塗装
後耐食性を改善することを目的として鋭意研究を重ねた
結果、Al水酸化物および/またはAl酸化物を含有す
るZn系めっき層を蒸着Al−Tiめっき層上に形成す
れば優れた塗装後耐食性が得られることを見い出した。
この塗装後耐食性は、下層側の蒸着Al−Ti合金めっ
きの優れた耐食性と上層側のZn系めっきの優れたりん
酸塩処理性が相俟ってはじめて達成できたものである。
以下本発明の蒸着Al−Tiめっき鋼板に関する各限定
理由について述べる。[Function] As a result of extensive research aimed at improving the post-painting corrosion resistance of vapor-deposited Al-Ti plated steel sheets, the present inventors found that a Zn-based plating layer containing Al hydroxide and/or Al oxide was used. It has been found that excellent post-painting corrosion resistance can be obtained by forming it on a vapor-deposited Al--Ti plating layer. This post-painting corrosion resistance could only be achieved by the combination of the excellent corrosion resistance of the vapor-deposited Al--Ti alloy plating on the lower layer side and the excellent phosphate treatment properties of the Zn-based plating on the upper layer side. The reasons for each limitation regarding the vapor deposited Al-Ti plated steel sheet of the present invention will be described below.
【0009】下層側の蒸着Al−Ti合金めっきの組成
は、Ti含有量が1〜20%の範囲であることを必要と
する。該Ti含有量が1%未満ではTi添加による耐食
性改善効果が不十分であり、一方多過ぎるとめっき層の
鋼素地に対する防食効果が減少し、いずれも十分な耐食
性性能は発揮できない。また上記蒸着Al−Tiめっき
層の付着量についても耐食性の面から1g/m2以上必
要である。The composition of the vapor-deposited Al--Ti alloy plating on the lower layer side requires a Ti content in the range of 1 to 20%. If the Ti content is less than 1%, the effect of improving corrosion resistance by adding Ti is insufficient; on the other hand, if it is too large, the corrosion-preventing effect of the plating layer on the steel substrate decreases, and in either case, sufficient corrosion resistance performance cannot be exhibited. Further, the amount of the vapor-deposited Al--Ti plating layer is also required to be 1 g/m2 or more from the viewpoint of corrosion resistance.
【0010】一方上層側のZn系めっきは、めっき層中
のAl水酸化物やAl酸化物がりん酸塩皮膜形成時の核
として作用すると共に、絶縁性を高めるので塗装後耐食
性向上効果も発揮する。但しAl水酸化物および/また
はAl酸化物の含有量が少な過ぎると緻密なりん酸塩皮
膜を形成することが困難であり、塗装後耐食性の大幅な
向上は望めない。Al水酸化物および/またはAl酸化
物の含有量が多過ぎるとりん酸塩処理の反応性自身が低
下すると共に、めっき層が脆くなってパウダリング現象
が起こりやすくなる。従ってめっき層中のAl水酸化物
および/またはAl酸化物の含有量は1〜20%とする
ことが必要であり、2〜15%が好ましい。尚上記Zn
系めっき層中に、Fe,Ni,Co,Ti,Mnなどの
元素を含有してもよく、Al水酸化物および/またはA
l酸化物の含有量が上記範囲内であれば同様の塗装後耐
食性改善効果が期待できる。On the other hand, the Zn-based plating on the upper layer side has the effect of improving corrosion resistance after painting because the Al hydroxide and Al oxide in the plating layer act as nuclei during the formation of a phosphate film and improve insulation. do. However, if the content of Al hydroxide and/or Al oxide is too low, it will be difficult to form a dense phosphate film, and a significant improvement in corrosion resistance after painting cannot be expected. If the content of Al hydroxide and/or Al oxide is too large, the reactivity of the phosphate treatment itself decreases, and the plating layer becomes brittle, making it easier to cause powdering. Therefore, the content of Al hydroxide and/or Al oxide in the plating layer needs to be 1 to 20%, preferably 2 to 15%. In addition, the above Zn
The system plating layer may contain elements such as Fe, Ni, Co, Ti, Mn, etc., and may contain Al hydroxide and/or A
If the content of l oxide is within the above range, a similar effect of improving corrosion resistance after painting can be expected.
【0011】上記Zn系めっきの付着量については0.
1 〜3g/m2であることが必要であり、0.5 〜
2g/m2が好ましい。上記付着量が少な過ぎるとZn
系めっき層のりん酸塩処理性改善効果が十分発揮できな
い。一方付着量が多過ぎるとりん酸塩処理後も上層めっ
き層が残存する可能性が生じ、残存した場合には腐食環
境下において上層Zn系めっきが優先的に溶解し、塗膜
ふくれが発生しやすくなる為塗装後耐食性は劣化する。[0011] The amount of Zn-based plating deposited is 0.
It is necessary to be 1 to 3 g/m2, and 0.5 to 3 g/m2.
2 g/m2 is preferred. If the above adhesion amount is too small, Zn
The effect of improving the phosphate treatment properties of the system plating layer cannot be fully demonstrated. On the other hand, if the amount of coating is too large, there is a possibility that the upper layer plating layer will remain even after the phosphate treatment, and if it remains, the upper layer Zn-based plating will preferentially dissolve in a corrosive environment, causing paint film blistering. Corrosion resistance deteriorates after painting.
【0012】0012
【実施例】清浄処理後の冷延鋼板上に10−2Paの真
空中、基板温度300 ℃で表1及び表2に示す種々の
組成及び付着量のAl−Tiめっきを蒸着した。次に大
気中に取り出してZnやAl等のイオンを含有する溶液
中で電気めっき或は置換めっきすることにより、Zn系
めっき層を上層に形成した。尚上記Zn系めっきの組成
は浴中のイオン濃度を変化させ、また付着量はめっき時
間を変化させることにより調整した。[Example] Al-Ti plating having various compositions and coating amounts shown in Tables 1 and 2 was deposited on a cold-rolled steel sheet after cleaning treatment in a vacuum of 10-2 Pa at a substrate temperature of 300°C. Next, a Zn-based plating layer was formed on the upper layer by taking it out into the atmosphere and performing electroplating or displacement plating in a solution containing ions such as Zn and Al. The composition of the Zn-based plating was adjusted by changing the ion concentration in the bath, and the amount of adhesion was adjusted by changing the plating time.
【0013】この様にして得た試験片について市販の浸
漬型りん酸塩処理を行った後、カチオン型電着塗装、中
塗り、上塗の3コート層(全塗膜厚100 μm )を
形成して下記の方法により塗装後耐食性を判定した。[0013] After subjecting the thus obtained test piece to a commercially available immersion type phosphate treatment, three coat layers (total coating thickness 100 μm) of cationic electrodeposition coating, intermediate coating, and top coating were formed. The corrosion resistance after painting was determined by the following method.
【0014】(塗膜密着性)40℃のイオン交換水に2
40 h浸漬した後2mm角ゴバン目100 個を入れ
、テープ剥離試験後の塗膜剥離個数で評価した。
○:剥離個数 0/100
△:剥離個数 1/100 〜5/100×:剥離個
数 6/100 以上(Coating film adhesion) 2 in ion exchange water at 40°C
After 40 hours of immersion, 100 2 mm square goblets were placed in the sample, and evaluation was made based on the number of peeled coatings after a tape peel test. ○: Number of peeled pieces 0/100 △: Number of peeled pieces 1/100 to 5/100×: Number of peeled pieces 6/100 or more
【0015】(耐塗膜ふくれ性)クロスカット後、塩水
噴霧試験を1000h行い、カット部からの塗膜ふくれ
幅で評価した。
○:ふくれ幅 3mm以下
△:ふくれ幅 3〜6mm
×:ふくれ幅 6mm以上(Resistance to paint film blistering) After cross-cutting, a salt water spray test was conducted for 1000 hours, and the width of the paint film blistering from the cut portion was evaluated. ○: Bulge width 3 mm or less △: Bulge width 3 to 6 mm ×: Bulge width 6 mm or more
【0016】(耐糸錆性)クロスカット後、塩水噴霧試
験(35℃×24h)、湿潤試験(40℃,80%RH
×120 h)、乾燥(RT×24h)を4サイクル実
施し、カット部からの糸錆長さで評価した。
○:糸錆長さ 2mm以下
△:糸錆長さ 2〜5mm
×:糸錆長さ 5mm以上
結果は表1及び表2に示す。(Thread rust resistance) After cross-cutting, salt spray test (35°C x 24h), humidity test (40°C, 80% RH)
x 120 h) and drying (RT x 24 h) for 4 cycles, and the length of thread rust from the cut portion was evaluated. ○: Thread rust length 2 mm or less Δ: Thread rust length 2 to 5 mm ×: Thread rust length 5 mm or more The results are shown in Tables 1 and 2.
【0017】[0017]
【表1】[Table 1]
【0018】[0018]
【表2】[Table 2]
【0019】No.1〜8は本発明に係る実施例であり
、塗膜密着性,耐塗膜ふくれ性及び耐糸錆性のすべてに
おいて優れている。[0019]No. Examples 1 to 8 are examples according to the present invention, which are excellent in all of coating film adhesion, coating film blistering resistance, and thread rust resistance.
【0020】No.9〜19は本発明に係る条件の1つ
または2つ以上を満足していない比較例であり、塗膜密
着性,耐塗膜ふくれ性及び耐糸錆性のうち少なくとも1
つが不十分である。[0020]No. Nos. 9 to 19 are comparative examples that do not satisfy one or more of the conditions according to the present invention, and at least one of paint film adhesion, paint film blistering resistance, and thread rust resistance.
is insufficient.
【0021】[0021]
【発明の効果】本発明は以上のように構成されているの
で、塗装後耐食性の優れた蒸着Al−Tiめっき鋼板が
提供できることとなり、耐食性に優れた蒸着Al−Ti
めっき鋼板を自動車や家電製品等に用いるパネル材に適
用できることとなった。Effects of the Invention Since the present invention is constructed as described above, it is possible to provide a vapor-deposited Al-Ti plated steel sheet with excellent corrosion resistance after painting.
It has become possible to apply plated steel sheets to panel materials used in automobiles, home appliances, etc.
Claims (1)
、以下同じ)含有する蒸着Al−Ti合金めっき層が1
g/m2以上形成され、その上層にAl水酸化物および
/またはAl酸化物を1〜20%含有するZn系めっき
が0.1 〜3g/m2形成されてなることを特徴とす
る塗装後耐食性に優れた蒸着Al−Tiめっき鋼板。Claim 1: 1 to 20% (wt%) of Ti on the surface of the steel plate.
, hereinafter the same) contains a vapor-deposited Al-Ti alloy plating layer of 1
Corrosion resistance after painting, characterized in that Zn-based plating containing 1 to 20% of Al hydroxide and/or Al oxide is formed on the top layer of 0.1 to 3 g/m2. Vapor-deposited Al-Ti plated steel sheet with excellent properties.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14240191A JPH04341579A (en) | 1991-05-18 | 1991-05-18 | Vapor-deposited al-ti plated steel sheet excellent in corrosion resistance after coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14240191A JPH04341579A (en) | 1991-05-18 | 1991-05-18 | Vapor-deposited al-ti plated steel sheet excellent in corrosion resistance after coating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04341579A true JPH04341579A (en) | 1992-11-27 |
Family
ID=15314492
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14240191A Withdrawn JPH04341579A (en) | 1991-05-18 | 1991-05-18 | Vapor-deposited al-ti plated steel sheet excellent in corrosion resistance after coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04341579A (en) |
-
1991
- 1991-05-18 JP JP14240191A patent/JPH04341579A/en not_active Withdrawn
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2002187234A (en) | Non-chromium coated steel plate having excellent corrosion resistance | |
JP3567430B2 (en) | Painted metal plate with excellent corrosion resistance | |
JPH055899B2 (en) | ||
JP4267213B2 (en) | Zinc phosphate-treated zinc-coated steel sheet with excellent corrosion resistance and color tone | |
JPH05214544A (en) | Highly corrosion-resistant galvanized steel sheet and its production | |
JPH04341578A (en) | Vapor-deposited al-cr plated steel sheet excellent in corrosion resistance after coating | |
JPH04341579A (en) | Vapor-deposited al-ti plated steel sheet excellent in corrosion resistance after coating | |
JPH11140665A (en) | Coated steel sheet excellent in edge face corrosion resistance and its production | |
JP3810677B2 (en) | Coating plate, surface preparation method of coating plate and method of manufacturing coated steel plate with excellent corrosion resistance | |
JP2575719B2 (en) | High corrosion resistant Zn-Mg alloy plated metal material for forming | |
JP3903900B2 (en) | Non-chromium zinc phosphate treated steel plate with excellent corrosion resistance, paint adhesion and workability | |
JP2787365B2 (en) | Organic thin film coated Cr-containing zinc-based multi-layer rust-proof steel sheet having excellent long-term adhesion of organic thin film and cationic electrodeposition coating property, and method for producing the same | |
JPH01116062A (en) | Zn-based multilayered vapor-deposited plating material excellent in corrosion resistance on uncoated or coated metallic base material | |
JP3845445B2 (en) | High corrosion-resistant surface-treated steel sheet and manufacturing method thereof | |
JP3900070B2 (en) | Non-chromic treatment of galvanized steel sheet | |
KR100276336B1 (en) | The al-silico oxide composite sheet and the same method | |
JPH0432576A (en) | Solution for zinc phosphate chemical conversion treatment | |
JP3478210B2 (en) | Resin chromate treated metal plate | |
JP3643475B2 (en) | Surface-treated steel sheet with excellent corrosion resistance | |
JPH04218660A (en) | High corrosion resistant zn-si vapor deposition plated metallic material | |
JPH04136199A (en) | Surface treated steel sheet excellent in corrosion resistance after being coated | |
KR100198048B1 (en) | Alloy coating sheet with sn-mn | |
JP2000313967A (en) | Surface treated steel sheet excellent in corrosion resistance | |
JP2004238699A (en) | Surface-conditioning method, non-chromium coated original sheet and production method of non-chromium coated steel sheet | |
JPH0225563A (en) | Manufacture of zinc-ti composite-plated steel sheet excellent in bare and after-painting corrosion resistance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980806 |