JPH03104633A - Surface-treated steel stock excellent in corrosion resistance - Google Patents
Surface-treated steel stock excellent in corrosion resistanceInfo
- Publication number
- JPH03104633A JPH03104633A JP24322589A JP24322589A JPH03104633A JP H03104633 A JPH03104633 A JP H03104633A JP 24322589 A JP24322589 A JP 24322589A JP 24322589 A JP24322589 A JP 24322589A JP H03104633 A JPH03104633 A JP H03104633A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- film
- corrosion resistance
- aluminum
- treatment
- 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.)
- Pending
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 57
- 239000010959 steel Substances 0.000 title claims abstract description 57
- 230000007797 corrosion Effects 0.000 title claims abstract description 44
- 238000005260 corrosion Methods 0.000 title claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 38
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 50
- 238000007747 plating Methods 0.000 claims description 35
- 229920000620 organic polymer Polymers 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 3
- 238000007654 immersion Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 66
- 239000003973 paint Substances 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002048 anodisation reaction Methods 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000013034 phenoxy resin Substances 0.000 description 2
- 229920006287 phenoxy resin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000005413 snowmelt Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐食性に優れた表面処理鋼材に関し、詳しく
は、アルミニウム系めっき層の上に、更にクロメート皮
膜層と有機高分子皮膜層を配したいわゆる有機複合めっ
き鋼材に関する．
（従来の技術）
自動車をはしめ建築等の分野では各種の表面処理鋼材が
使用されている．代表的なものは、亜鉛或いはＺｎ−Ｎ
ｉＳＺｒｉ−Ｆｅ．．Ｚｎ−Ｍｇ．．Ｚｎ−＾ｌ等の亜
鉛系合金を溶融めっき法、電気めっき法、真空蒸着法等
によりめっきした填材である．また、純アルミニウム或
いはｋｌ −Ｓｉ， Ａｌ−Ｍｎ、Ａｌ −Ｚｎ等のア
ルくニウム系合金を同様の方法でめっきした鋼材もこれ
らの分野で貫用されている．特に、後者の純アルミニウ
ム又はアルミニウム系合金をめっきした鋼材（以下、こ
れらを総称してアルミニウム系めっき鋼材と言う）は、
前者の亜鉛又は亜鉛系合金をめっきした鋼材（以下、こ
れらを総称して亜鉛系めっき鋼材と言う）に比べ、耐海
水性および耐熱性に優れているので、自動車の分野では
マフラーなどの排気系材料に、建築分野では海洋環境で
用いられる構造部材に大量に使用されている．中でもＡ
ｊ！−Ｍｎ合金めっき鋼材は、他のものと比べ、極めて
高い耐食性を示すので海洋環境下で多く使用されている
。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a surface-treated steel material with excellent corrosion resistance, and more specifically, a chromate film layer and an organic polymer film layer are further disposed on an aluminum plating layer. This paper relates to so-called organic composite plated steel materials. (Prior art) Various surface-treated steel materials are used in fields such as automobile construction and construction. Typical examples are zinc or Zn-N
iSZri-Fe. ．． Zn-Mg. ．． It is a filler plated with a zinc-based alloy such as Zn-^l by hot-dip plating, electroplating, vacuum evaporation, etc. In addition, steel materials plated with pure aluminum or aluminium-based alloys such as kl-Si, Al-Mn, Al-Zn, etc. in a similar manner are also commonly used in these fields. In particular, the latter steel materials plated with pure aluminum or aluminum-based alloys (hereinafter collectively referred to as aluminum-based plated steel materials),
Compared to the former steel materials plated with zinc or zinc-based alloys (hereinafter collectively referred to as zinc-based plated steel materials), it has superior seawater resistance and heat resistance, so it is used in exhaust systems such as mufflers in the automobile field. In the construction field, it is used in large quantities for structural members used in marine environments. Among them, A
j! -Mn alloy plated steel exhibits extremely high corrosion resistance compared to other materials, and is therefore widely used in marine environments.
ところが、近年、これら表面処理鋼材の使用環境が一段
と厳しくなる傾向にあり、それにともないより高い耐食
性を有する鋼材が求められている．例えば、自動車分野
では冬期に道路凍結防止用の溶雪塩を散布する北米等で
、車体の袋構造部、合わせ部或いは車体下部といった部
分での腐食が問題となっており、建築分野では塩水によ
る濡れ、乾きを繰り返す環境下や高湿度の環境下で鋼材
を使用するケースが増えてきているので、このような厳
しい腐食環境でも長期にわたり優れた耐食性を発揮する
鋼材が求められている．
（発明が解決しようとする！ＩＩ）
鋼材の耐食性を高めるには材料自体の改善或いは他の保
護皮膜の形成が考えられる．後者には亜鉛系めっき層の
上に、更にクロメート皮膜層と有機高分子皮膜層を配し
たいわゆる有機複合めっき鋼材がある．この有機複合め
っき鋼材は単層の亜鉛系めっき鋼材および単層のアルミ
ニウム系めっき鋼材に比べ、耐食性は遥かに優れている
が、それでも海洋環境下でのメンテナンスフリーの観点
から長期保証（例えば２０年）ができるまでの耐食性を
有していないと言われている。However, in recent years, the environments in which these surface-treated steel materials are used have become increasingly harsh, and as a result, steel materials with even higher corrosion resistance are required. For example, in the automotive field, corrosion of parts such as the bag structure, joints, and lower parts of the car body has become a problem in North America and other countries where snowmelt salt is sprayed to prevent roads from freezing in the winter.In the construction field, corrosion caused by salt water has become a problem. As steel materials are increasingly being used in environments that repeatedly wet and dry or in high humidity environments, there is a need for steel materials that can exhibit excellent corrosion resistance over a long period of time even in such severe corrosive environments. (What the invention attempts to solve! II) In order to increase the corrosion resistance of steel materials, it is possible to improve the material itself or to form other protective films. The latter includes so-called organic composite plated steel materials, which have a chromate film layer and an organic polymer film layer on top of the zinc-based plating layer. Although this organic composite plated steel material has much better corrosion resistance than single-layer zinc-based plated steel material and single-layer aluminum-based plated steel material, it still has a long-term guarantee (for example, 20 years) from the viewpoint of maintenance-free operation in the marine environment. ) is said to not have the corrosion resistance that is required.
本発明の課題は、厳しい腐食環境下で使用しても長期間
良好な銅食性を発揮することができる表面処理鋼材を提
供することにある．具体的には本発明は自動車用、海洋
構造物、橋梁等に好適なアルミニウムめっき層を有した
高耐食性を示す有機複合めっき鋼材を提供することを目
的とする。An object of the present invention is to provide a surface-treated steel material that can exhibit good copper corrosion resistance for a long period of time even when used in a severe corrosive environment. Specifically, an object of the present invention is to provide an organic composite plated steel material having an aluminum plating layer and exhibiting high corrosion resistance, which is suitable for automobiles, marine structures, bridges, etc.
（課題を解決するための手段）
前掲の亜鉛系めっき鋼材を母材とした有機複合めっき鋼
材は、単層の亜鉛系めっき鋼材および単層のアルミニウ
ム系めっき鋼材より耐食性は優れている。そこで、本発
明者らは母材めっき鋼材に亜鉛系めっき鋼材より高耐食
性を有するアルξニウム系めっき鋼材を使用すれば、耐
食性がより向上するのではないかと考え、このような有
機複合めっき鋼材を試作した。この鋼材は確かに亜鉛系
めっきの有機複合鋼材より耐食性はよいものの長期保証
が可能なまでの耐食性を有していないが、同様の皮膜構
成をとったもので、第一層のアルミニウム系めっき層を
陽極酸化処理したものは著しく高い耐食性を示すことが
判明した．
本発明はこのような知見を基に完威したものであって、
その要旨は「鋼材の表面に、第一層として付着量で１〜
１５０ｇ／ｍ”の表面が陽極酸化処理されたアルミニウ
ム系めっき層を有し、その上に、第二層として付着量が
ｃｒｔｌａ算で１０〜３００＋ｓｇ／ｍ”のクロメート
皮１１ｍ！層を有し、第三層として皮膜厚が０．３μｍ
以生の有機高分子皮膜層を有することを特徴とする耐食
性に優れた表面処理鋼材」にある．本発明の表面処理鋼
材は、前記第一層の陥極酸化処理されたアルミニウム系
めっき層が、封孔処理されたものであることが望ましい
。(Means for Solving the Problems) The organic composite plated steel material using the above-mentioned zinc-based plated steel material as a base material has superior corrosion resistance to single-layer zinc-based plated steel material and single-layer aluminum-based plated steel material. Therefore, the present inventors thought that corrosion resistance could be further improved by using aluminum-plated steel, which has higher corrosion resistance than zinc-based plated steel, as the base plated steel, and developed such organic composite plated steel. We made a prototype. Although this steel material certainly has better corrosion resistance than zinc-plated organic composite steel material, it does not have the corrosion resistance to warrant a long-term guarantee, but it has a similar coating structure, with the first aluminum plating layer It was found that the anodized material showed significantly high corrosion resistance. The present invention was developed based on such knowledge, and
The gist of this is ``On the surface of the steel material, as the first layer, the coating amount is 1~1~
It has an aluminum plating layer with an anodized surface of 150g/m", and on top of that, 11m of chromate skin with a coating weight of 10~300+sg/m" as a second layer! The third layer has a film thickness of 0.3 μm.
``Surface-treated steel material with excellent corrosion resistance characterized by having an organic polymer film layer''. In the surface-treated steel material of the present invention, it is preferable that the first layer of the aluminum-based plating layer subjected to the pit oxidation treatment is subjected to a sealing treatment.
（作用） 以下、添付図面を参照して本発明を詳細に説明する。(effect) Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
第１図は、本発明の表面処理鋼材を示す断面拡大図であ
る．
この表面処理鋼材は、例えば、熱延鋼板、冷延鋼板、厚
鋼板、形鋼等の鋼材（或いは、これらを更に加工した鋼
材）１の表面に、第一層としてアルごニウム系めっき層
２を有し、その上に、第二層としてクロメート皮膜層３
を有し、第三層として有機高分子皮膜層４を有するもの
である。FIG. 1 is an enlarged cross-sectional view showing the surface-treated steel material of the present invention. This surface-treated steel material includes, for example, an argonium-based plating layer 2 as a first layer on the surface of a steel material 1 such as a hot-rolled steel plate, a cold-rolled steel plate, a thick steel plate, or a shaped steel (or a steel material obtained by further processing these). and a chromate film layer 3 as a second layer thereon.
and has an organic polymer film layer 4 as the third layer.
前記第一層のアルミニウム系めっき層２とは、純アルミ
ニウム又はＡＮ −Ｓｉ， Ａｊ！−Ｍｎ、Ａｆｆｉ−
Ｚｎ，Ａｌ−ＴｉＳＡｊ！−Ｃｒ等であって、アルミニ
ウムを主威分とする合金をめっきしたものである．アル
ミニウム系めっきＮ２は、溶融めっき法、電気めっき法
、真空蒸着法、等により形成することができる．
本発明では、このアルミニウム系めっき層２は、陽極酸
化処理により皮膜が改質されている。従って、その皮膜
は、第１図に示すように多数の小孔５を有するボーラス
層となっている．アル藁ニウム系めっき層２の改質は、
いずれの陽極酸化法で行ってもよい．例えば、通電方法
として直流法、交流法、交直重畳法等があるが、これら
いずれの方法でもアルミニウム系めっき層２を改質する
ことができる．また、電解液については硫酸、シ１ウ酸
、クロム酸、リン酸等の酸浴、水酸化アルカリ、アンモ
ニアーフッ化物等のアルカリ浴、或いはこれらの混合浴
等があるが、いずれの種類の浴を使用してもよい．なお
、皮膜の着色処理を行う場合は、陽極酸化処理後に自然
発色しない、例えば、硫酸、ホウ酸浴等を使用するのが
よい。The first aluminum plating layer 2 is pure aluminum or AN-Si, Aj! -Mn, Affi-
Zn, Al-TiSAj! -It is plated with an alloy such as Cr, whose main component is aluminum. The aluminum-based plating N2 can be formed by a hot-dip plating method, an electroplating method, a vacuum evaporation method, or the like. In the present invention, the coating of this aluminum-based plating layer 2 is modified by anodic oxidation treatment. Therefore, the film is a bolus layer having a large number of small holes 5 as shown in FIG. The modification of the aluminum plating layer 2 is as follows:
Any anodic oxidation method may be used. For example, there are a direct current method, an alternating current method, an alternating current method, an AC/DC superimposition method, etc. as the current application method, and the aluminum-based plating layer 2 can be modified by any of these methods. Regarding the electrolyte, there are acid baths such as sulfuric acid, citric acid, chromic acid, phosphoric acid, alkaline baths such as alkali hydroxide, ammonia fluoride, etc., or mixed baths of these. You may use a bath. When coloring the film, it is preferable to use a bath that does not naturally develop color after anodizing, such as a sulfuric acid bath or a boric acid bath.
アルミニウム系めっき層２の付着量は、１〜１５０ｇ
／ｅａ ２が適当である。この範囲内の付着量であれば
高耐食性が得られるが、１ ｇ／ｓ＋”より少ない付着
量では赤錆の発生に至るまでの時間が非常に短く、素地
鋼材に対する防食性が充分でない。一方、１５０ｇ ／
ｖａ ｔを超えてめっきしても耐食性の向上効果が飽和
するのみならず、溶接性の劣化、加工性の劣化、重量増
等の問題が生じる。望ましい付着量は１０〜６０ｇ／ｍ
”である。The amount of aluminum plating layer 2 deposited is 1 to 150 g.
/ea 2 is appropriate. If the coating amount is within this range, high corrosion resistance can be obtained, but if the coating amount is less than 1 g/s+'', the time until red rust occurs is very short, and the corrosion protection against the base steel is not sufficient.On the other hand, 150g/
Even if plating exceeds vat, not only the effect of improving corrosion resistance is saturated, but also problems such as deterioration of weldability, deterioration of workability, and increase in weight occur. Desired coating weight is 10-60g/m
” is.
第二層のクロメート皮ＩＦＩ層３は、通常のクロメート
処理液を用いて、スブレイ処理、浸漬処理、ロール塗布
処理、電解処理等の通常の処理方法でアルミニウム系め
っき層２の表面に形或することができる。また，、その
皮膜組成についても特に規定する必要がないが、皮膜厚
が過度に薄いと充分な耐食性が得られず、厚過ぎると塗
装後の耐食性が劣化するので、Ｃｒ換算で１０〜３００
ｍｇ／ｍ”の付着量とするのがよい。より望ましいのは
Ｃｒ換算で４０〜２００ｍｇ／ｍ”である。The second chromate skin IFI layer 3 is formed on the surface of the aluminum plating layer 2 by using a normal chromate treatment solution and a normal treatment method such as scrubbing treatment, dipping treatment, roll coating treatment, electrolytic treatment, etc. be able to. There is no need to specify the composition of the coating, but if the coating is too thin, sufficient corrosion resistance will not be obtained, and if it is too thick, the corrosion resistance after painting will deteriorate.
The adhesion amount is preferably 40 to 200 mg/m'' in terms of Cr.
第三層は有機高分子の塗料を塗布した皮膜層４である．
塗料には常温乾燥型、焼付乾燥型、放射線硬化型等の各
種の塗料があるが、本発明では焼付硬化型塗料を使用し
て第三層を形威してやるのが特に好ましい．これは、焼
付硬化型塗料はもともと耐食性が優れているうえに、下
層のクロメート皮膜の表層に微量に存在している６価ク
ロムにより焼付中に塗料中の樹脂が酸化され、塗膜と下
層クロメート皮膜との密着性が向上し、耐食性が一層よ
くなるからである．このような焼付硬化型塗料の代表例
としては、エボキシ樹脂塗料、フエノキシ樹脂塗料、ボ
リアミド樹脂塗料、アクリル樹脂塗料等が挙げられる。The third layer is film layer 4 coated with an organic polymer paint.
There are various types of paints, such as room temperature drying type, bake drying type, and radiation curing type, but in the present invention, it is particularly preferable to use a bake cure type paint to form the third layer. This is because bake-curable paints have excellent corrosion resistance, and the resin in the paint is oxidized during baking due to trace amounts of hexavalent chromium present on the surface of the underlying chromate film, causing the paint film and the underlying chromate film to oxidize. This is because the adhesion with the film improves, resulting in even better corrosion resistance. Typical examples of such bake-curable paints include epoxy resin paints, phenoxy resin paints, polyamide resin paints, acrylic resin paints, and the like.
この塗料は、乾燥後に膜ＦＪ０．３μ口以上の有機高分
子皮膜が得られるように塗装するのがよい．膜厚が０、
３μｍ未満では、有機皮膜を形或することによる耐食性
向上効果が不十分である．性能上の膜厚の上限はないが
、望ましい有機高分子皮膜層の膜厚は、０．７〜３０μ
ｍである。This paint should be applied so that an organic polymer film with a film FJ of 0.3 μm or more is obtained after drying. Film thickness is 0,
If the thickness is less than 3 μm, the effect of improving corrosion resistance by forming an organic film is insufficient. Although there is no upper limit to the film thickness in terms of performance, the desirable film thickness of the organic polymer film layer is 0.7 to 30 μm.
It is m.
第２図は、本発明のもう一つの表面処理鋼材を示す断面
拡大図である．
この表面処理鋼材は、その皮膜構或は前記と同しである
．異なる点は、第一層の陽極酸化処理されたアルミニウ
ム系めっき層２が、更に封孔処理されていることにある
。FIG. 2 is an enlarged cross-sectional view showing another surface-treated steel material of the present invention. This surface-treated steel material has the same coating structure as described above. The difference lies in that the first layer, the anodized aluminum plating layer 2, is further subjected to a sealing treatment.
陽極酸化処理したままのアルミニウム系めっき層２は、
多数の小孔（５）を有するボーラス層であるが、封孔処
理して孔の入口を塞いでやれば母材を保護する性能が一
段と向上し、腐食が生しにくくなる．
封孔処理は、例えば、化学的方法の水和封孔、無機質封
孔、有機質封孔、或いは電気化学的方法の無機質封孔、
有ａ質封孔、等のいずれの方法で実施してもよい．
以上説明した陽極電解処理されたアルξニウム系めっき
層２の上に、クロメート皮膜層３と有機高分子皮膜層４
を有する第１発明の表面処理鋼材は、従来の単層の亜鉛
系めっき鋼材および単層のアルミニウム系めっき鋼材よ
り耐食性が遥かに優れていることは勿論、亜鉛系めっき
をベースとした有機複合鋼材と比べても高い耐食性を有
している．さらに封孔処理したアルξニウム系めっき層
を有する第２発明の・表面処理鋼板は、これよりも一段
と優れた耐食性を有する．
以下、実施例により本発明を更に説明する。The aluminum-based plating layer 2 that has been anodized is
The bolus layer has many small pores (5), but if the pore entrances are closed by sealing, the ability to protect the base material will be further improved and corrosion will be less likely to occur. The sealing treatment includes, for example, hydration sealing using a chemical method, inorganic sealing, organic sealing, or inorganic sealing using an electrochemical method.
It may be carried out by any method such as aerobic sealing. On top of the anodic electrolytically treated aluminum plating layer 2 described above, a chromate film layer 3 and an organic polymer film layer 4 are formed.
The surface-treated steel material of the first invention has far superior corrosion resistance than conventional single-layer zinc-based plated steel material and single-layer aluminum-based plated steel material, as well as organic composite steel material based on zinc-based plating. It has high corrosion resistance compared to Furthermore, the surface-treated steel sheet of the second invention, which has a sealed aluminum plating layer, has even better corrosion resistance than this. The present invention will be further explained below with reference to Examples.
（実施例）
母材に０．８＋＋ｖ＋厚の冷延鋼板を使用し、表面を脱
脂および酸洗処理した後、溶融浸漬めっき法、電気めっ
き、真空蒸着法のいずれかの方法で純Ａｌ（９Ｑ．８％
＾ｉ）、ＡＮ−８重量％Ｓｉ合金、Ａｌ−２５重量％Ｍ
ｎ合金のいずれかのめっき皮膜を形威した。(Example) A cold-rolled steel plate with a thickness of 0.8++v+ was used as the base material, and after the surface was degreased and pickled, pure Al (9Q .8%
^i), AN-8 wt% Si alloy, Al-25 wt% M
A plating film of one of the n-alloys was formed.
次いで、下記の条件で陽極酸化処理、或いは陽極酸化処
理と封孔処理を行ってから、ＣｒＯｓ：２０ｇ／ １、
ＨｓＰＯ４： ２ ｇ／ ｌを含有ずるクロメート液を
使用し、浸漬法で前記めっき層の上にクロメート皮膜層
を形成し、さらに、このクロメート皮膜の上に、高分子
量フェノキシ樹脂塗料（商品名Ｂａｋｅｌ ｉ ｔｅＰ
Ｋ｝Ｉ｝ｌ，ユニオン・カーバイド社製）を塗布し、板
温度２５０℃で６０秒間焼付して塗膜を硬化させ、有機
高分子皮膜層を形威した。Next, after performing anodization treatment or anodization treatment and sealing treatment under the following conditions, CrOs: 20g/1,
A chromate film layer is formed on the plating layer by a dipping method using a chromate solution containing 2 g/l of HsPO4, and then a high molecular weight phenoxy resin paint (trade name Bakeri) is applied on top of this chromate film. teP
K}I}l (manufactured by Union Carbide) was applied and baked at a plate temperature of 250° C. for 60 seconds to cure the coating film and form an organic polymer film layer.
比較例として、アルｅニウム系めっき層の上にクロメー
ト皮膜層と有機高分子皮膜層を有しているが、アルミニ
ウム系めっき層が陽極酸化処理されていないもの、陽極
酸化処理されたアルミニウム系めっき層のみのもの、陽
極酸化処理されたアルミニウム系めっき層とクロメート
皮膜層からなるものおよびアルミニウム系めっき層、ク
ロメート層或いは有機高分子皮膜層の付着量のいずれか
が、本発明で規定する付着量の範囲を外れたものも作威
した．
〔陽極酸化処理条件〕
硫酸１５％の水溶液を使用し、液点２０℃に保って６０
Ｖの交流を１分間通電．
〔封孔処理条件〕
９５〜ｌ００゜Ｃの沸騰水にｌＯ分間浸漬。As a comparative example, a chromate film layer and an organic polymer film layer are provided on an aluminum plating layer, but the aluminum plating layer is not anodized, and an anodized aluminum plating layer is used. A layer only, a layer consisting of an anodized aluminum plating layer and a chromate film layer, and an amount of the aluminum plating layer, chromate layer, or organic polymer film layer specified in the present invention. It has also been used to create works that are outside the scope of the above. [Anodizing treatment conditions] Using a 15% sulfuric acid aqueous solution, keeping the liquid point at 20°C,
Apply AC current of V for 1 minute. [Sealing treatment conditions] Immersed in boiling water at 95 to 100°C for 10 minutes.
このようにして作威した供試材について、未加工の平板
のまま、および直径５０ａｉｍの円筒絞り加工を行った
ものの耐食性を調べた。円筒絞りではダイス肩は、その
表面粗さが常に一定となるように、各回ごとにトリクロ
口エタンによる洗浄と１２０番エメリー祇による研磨を
行った．
耐食性は、上記試験片に対して、塩水噴霧（５％ＮａＣ
ｌ、３５”Ｃ）Ｘ２時間→乾燥（５０’Ｃ）Ｘ２時間
一相対湿度９５％以上の湿潤雰囲気放置（５０゜Ｃ）×
４時間を１サイクルとする乾湿繰り返し促進耐食性試験
を行い、試験片の赤錆発生状況を観察することで評価し
た。第１表に試験結果と第一層のめっき方法、めっき皮
膜組戊、付＠量、第二層のクロメート付着量、第三層の
有機高分子皮膜の膜厚をまとめて示す。The corrosion resistance of the test materials produced in this way was investigated, both as unprocessed flat plates and after drawing into a cylinder with a diameter of 50 aim. In the cylindrical drawing, the die shoulder was cleaned with trichome ethane and polished with No. 120 emery after each use, so that the surface roughness was always constant. Corrosion resistance was measured using salt water spray (5% NaC) on the above test piece.
l, 35"C) x 2 hours → Dry (50'C) x 2 hours - Leave in a humid atmosphere with relative humidity of 95% or more (50°C) x
An accelerated corrosion resistance test was carried out with repeated wet and dry cycles of 4 hours, and evaluation was made by observing the occurrence of red rust on the test pieces. Table 1 summarizes the test results, the plating method for the first layer, the plating film composition, the coating amount, the amount of chromate deposited in the second layer, and the thickness of the organic polymer film in the third layer.
第ｌ表における耐食性の評価基準は次の通りである。The evaluation criteria for corrosion resistance in Table 1 are as follows.
◎：４００サイクル経過後も赤錆発生が認められないも
の、
○：３００サイクル前後で赤錆発生が始まるもの、△：
２００サイクルまでに赤錆発生が見られるもの、
ｘ ： １００サイクルまでに赤錆発生が見られるもの
．
（以下、余白）
第ｌ表から明らかなように、比較例の表面処理鋼材は耐
食性に劣るが、本発明例の表面処理鋼材はいずれも耐食
性に優れ、少なくとも３００サイクル前後以上にならな
いと赤錆が発生しない．特にこの中でも第一層のアル逅
ニウム系めっき層を陽極酸化処理し、更に封孔処理した
ものは、４００サイクル経過後でも赤錆発生が認められ
ない。◎: No red rust is observed even after 400 cycles, ○: Red rust begins to occur around 300 cycles, △:
Items where red rust formation is observed by 200 cycles. x: Items where red rust formation is observed by 100 cycles. (Hereinafter, blank spaces) As is clear from Table 1, the surface-treated steel materials of the comparative examples have poor corrosion resistance, but the surface-treated steel materials of the present invention examples all have excellent corrosion resistance, and red rust occurs only after at least 300 cycles. Does not occur. Particularly among these, in the case where the first aluminum-based plating layer was anodized and further sealed, no red rust was observed even after 400 cycles.
（発明の効果）
本発明の表面処理鋼材は、実施例のような厳しい促進耐
食性試験においても高い耐食性を示すので、自動車にお
ける袋構造部、合わせ部、車体下部等の部材、また海洋
構造物や橋梁等に使用しても長期間にわたって腐食に耐
えることができる。(Effects of the Invention) The surface-treated steel of the present invention exhibits high corrosion resistance even in severe accelerated corrosion resistance tests such as those in Examples, so it can be used for parts such as bag structures, mating parts, and lower body parts of automobiles, as well as marine structures. Even when used in bridges, etc., it can withstand corrosion for a long period of time.
２：第一層 ３：第二層 ４：第三層 ５：小孔 （アルミニウム系めっき層） （クロメー１・皮膜層） （有機高分子皮膜層）2: First layer 3: Second layer 4: Third layer 5: Small hole (Aluminum plating layer) (Chrome 1/film layer) (Organic polymer film layer)
Claims (2)
ｇ／ｍ＾２で表面が陽極酸化処理されたアルミニウム系
めっき層を有し、その上に、第二層として付着量がＣｒ
換算で１０〜３００ｍｇ／ｍ＾２のクロメート皮膜層を
有し、第三層として皮膜厚が０．３μｍ以上の有機高分
子皮膜層を有することを特徴とする耐食性に優れた表面
処理鋼材。(1) The amount of the first layer deposited on the surface of the steel material is 1 to 150.
It has an aluminum plating layer whose surface is anodized with a coating weight of Cr.
A surface-treated steel material with excellent corrosion resistance, characterized by having a chromate film layer of 10 to 300 mg/m^2 in terms of conversion, and an organic polymer film layer having a film thickness of 0.3 μm or more as a third layer.
き層が、更に封孔処理されていることを特徴とする請求
項（１）記載の耐食性に優れた表面処理鋼材。(2) The surface-treated steel material with excellent corrosion resistance according to claim (1), wherein the first layer of anodized aluminum plating layer is further subjected to a sealing treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24322589A JPH03104633A (en) | 1989-09-18 | 1989-09-18 | Surface-treated steel stock excellent in corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24322589A JPH03104633A (en) | 1989-09-18 | 1989-09-18 | Surface-treated steel stock excellent in corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03104633A true JPH03104633A (en) | 1991-05-01 |
Family
ID=17100698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24322589A Pending JPH03104633A (en) | 1989-09-18 | 1989-09-18 | Surface-treated steel stock excellent in corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03104633A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001519482A (en) * | 1997-10-13 | 2001-10-23 | アルキャン・インターナショナル・リミテッド | Coated aluminum products |
| WO2007080849A1 (en) * | 2006-01-10 | 2007-07-19 | Mitsui Mining & Smelting Co., Ltd. | Method for chemical conversion treatment of the surface of aluminum material and aluminum material |
| EP2248662A1 (en) * | 2009-05-01 | 2010-11-10 | Fujifilm Corporation | Metal composite substrate and method of producing the same |
-
1989
- 1989-09-18 JP JP24322589A patent/JPH03104633A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001519482A (en) * | 1997-10-13 | 2001-10-23 | アルキャン・インターナショナル・リミテッド | Coated aluminum products |
| WO2007080849A1 (en) * | 2006-01-10 | 2007-07-19 | Mitsui Mining & Smelting Co., Ltd. | Method for chemical conversion treatment of the surface of aluminum material and aluminum material |
| JPWO2007080849A1 (en) * | 2006-01-10 | 2009-06-11 | 三井金属鉱業株式会社 | Chemical conversion treatment method for aluminum material surface and aluminum material |
| EP2248662A1 (en) * | 2009-05-01 | 2010-11-10 | Fujifilm Corporation | Metal composite substrate and method of producing the same |
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