JPH0512439B2 - - Google Patents
Info
- Publication number
- JPH0512439B2 JPH0512439B2 JP63118118A JP11811888A JPH0512439B2 JP H0512439 B2 JPH0512439 B2 JP H0512439B2 JP 63118118 A JP63118118 A JP 63118118A JP 11811888 A JP11811888 A JP 11811888A JP H0512439 B2 JPH0512439 B2 JP H0512439B2
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- cationic polymer
- plating
- weight
- composite electroplated
- 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
- 238000007747 plating Methods 0.000 claims description 36
- 238000005260 corrosion Methods 0.000 claims description 33
- 230000007797 corrosion Effects 0.000 claims description 32
- 229910000831 Steel Inorganic materials 0.000 claims description 31
- 239000010959 steel Substances 0.000 claims description 31
- 229920006317 cationic polymer Polymers 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011701 zinc Substances 0.000 description 26
- 239000010410 layer Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- 150000001412 amines Chemical group 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- -1 amine salts Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical group [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Description
（産業上の利用分野）
本発明は自動車、家電、建材等に使用される耐
食性および加工性に優れた防錆用の複合電気めつ
き鋼板に関する。
（従来の技術）
すでに冷延鋼板の耐食性、塗装後の耐食性の向
上及び加工性を損なわず量産化できる表面処理鋼
板として電気亜鉛めつき鋼板が汎用されているこ
とは周知である。
ところが近年では寒冷地帯における冬期の道路
凍結防止用の散布塩に対する自動車の防錆鋼板と
して亜鉛めつき鋼板の使用が試みられ、苛酷な腐
食環境での耐食性の要求が増加する傾向にある。
これら亜鉛めつき鋼板の耐食性の向上要求に対
して亜鉛のメツキ量（付着量）による耐食性の向
上が知られているが、メツキ量の増加以外の方法
として亜鉛自身の溶解を抑制するための合金メツ
キが数多く提案されている。これらの多くは、
Fe、Ni、Coといつた鉄族元素を合金成分として
含有するものである。
これらの亜鉛−鉄族系電気めつき鋼板は、例え
ば特公昭50−29821号公報、特公昭57−61831号公
報に見られるごとく、未塗装あるいは塗装後の耐
食性が優れる特徴があり、工業的に生産、実用さ
れているが、耐食性を更に向上されることが強く
望まれている。
ZnないしZn系合金めつき中にCrを含有させた
電気めつき鋼板として、例えば特公昭59−38313
及び59−40234号公報、特開昭61−130498、61−
270398、62−54099号公報等が開示されている。
これらは何れもCrの含有率が５％以下と微量
であつて、耐食性にとつてCrの効果は付随的で
しかあり得ない。従つて、耐食性を改善する目的
からは更に高含有量のCrを共析させることが強
く望まれるところである。
（発明が解決しようとする課題）
しかしながら、従来Cr含有率を高め得るZn−
Cr電気めつき技術がなかつた。即ち、単にめつ
き浴中の３価Crイオン濃度を高めても加工性の
良いめつきが得られず、電流効率も急減する等の
障害があつて工業的にCr含有率の高い電気めつ
き鋼板を得ることは極めて困難であつた。
本発明は、上記問題点に鑑み、従来にない高
Cr含有率の耐食性かつ加工性に優れた実用性の
高い複合電気めつき鋼板を提供するものである。
（課題を解決するための手段）
本発明は、Zn2+とCr3+を含むめつき浴に、水
溶性のカチオンポリマーを導入し、この作用で
Cr析出を促進することにより、従来にない高Cr
含有率を得ることができ、かつ、カチオンポリマ
ーの微量共析により、加工性をも確保することに
成功したものである。
本発明の要旨は、
〔１〕 鋼板の表面に、Crを５〜30重量％、め
つき液に添加した分子量103〜106の４級アミン
の重合物からなる水溶性カチオンポリマーを電
気的に析出せしめてなるカチオンポリマーを
0.005〜５重量％、残部Znとする複合電気めつ
き層を形成したことを特徴とする耐食性に優れ
た複合電気めつき鋼板。
〔２〕 鋼板の表面に、Crを５〜30重量％、め
つき液に添加した分子量103〜106の４級アミン
の重合物からなる水溶性カチオンポリマーを電
気的に析出せしめてなるカチオンポリマーを
0.005〜５重量％、残部Znとする複合電気めつ
き層を形成し、該複合電気めつき層の上層とし
てZnもしくはZn系合金めつき層を形成したこ
とを特徴とする耐食性に優れた複合電気めつき
鋼板。
である。
（作用）
本発明の複合電気めつき鋼板の耐食性は、主と
してCrの作用である。Cr含有率は、５〜30重量
％が好ましい。５重量％未満であれば、若干の効
果は認められるものの、赤錆が発生する傾向は残
り、耐食性は十分ではない。５重量％以上になる
と、例えば塩水噴霧試験等では赤錆発生が抑制さ
れ、画期的な効果が現われてくる。
このような高耐食性は、従来公知のZnめつき
あるいはZn−Fe、Zn−Ni等の合金めつきでは到
底達成することはできない。
CrはZnとの共存下では不働態化せず、Znとと
もに犠牲防食作用に加担し、しかもCrの腐食生
成物が難溶性の保護皮膜を腐食部に沈積すること
により、腐食を抑制していることが高耐食性を発
揮する理由であろうと考えられる。
Cr含有率が30重量％を超えると、耐食性は良
いものの、後述するカチオンポリマーの共析によ
る作用をもつても、プレス加工等の加工時にめつ
き層が剥離するいわゆるパウダリング性の劣化を
防止し得ず、実用上は適用が難しい。
カチオンポリマーは、Crの析出促進剤であり、
かつCrと共に微量めつき層内に共析することに
より、加工時の耐パウダリング性を向上させる。
このようなカチオンポリマーの共析効果は、Cr
イオンがZnの均一な電析成長を阻害し、均一性、
平滑性に欠けためつき構造となつてしまうことを
防止する点にあると推定される。即ち、共析した
カチオンポリマーを介することによつて、Znと
Crが均一に混合もしくは合金化した緻密なめつ
き層が形成されると考えられる、カチオンポリマ
ーの含有率としては、0.005〜５重量％が好まし
い。0.005重量％未満では、加工時の耐パウダリ
ング性に対して効果が乏しく、また５重量％超の
含有率は、めつき浴中のカチオンポリマー濃度を
増しても得られ難いのみならず、多量に共析する
と、めつき密着性が低下する原因となる。加工性
の観点からは、Cr含有率の1/1000以上の含有率
でカチオンポリマーが共析していれば十分であ
る。
本発明に用いる水溶性のカチオンポリマーは４
級アミンの重合物が効果的なポリマーであり、分
子量は、この場合、103〜106が望ましい。
次に示すアミンポリマーの内、ポリアミンスル
ホン（PASと略）およびポリアミン（PA）がCr
析出促進剤として最も効果的である。アミン基に
よる吸着作用とスルホン基との金属イオンもしく
は金属の結合が寄与していると考えられる。基本
的には、次に示す４級アミンの塩（アンモニウム
塩）
(Industrial Field of Application) The present invention relates to a composite electroplated steel sheet for rust prevention that has excellent corrosion resistance and workability and is used in automobiles, home appliances, building materials, etc. (Prior Art) It is well known that electrogalvanized steel sheets are already widely used as surface-treated steel sheets that can be mass-produced without impairing the corrosion resistance of cold-rolled steel sheets, the corrosion resistance after painting, and workability. However, in recent years, attempts have been made to use galvanized steel sheets as anti-corrosion steel sheets for automobiles in response to the salt sprayed on roads in winter to prevent roads from freezing in cold regions, and there is a tendency for demands for corrosion resistance in severe corrosive environments to increase. In response to these demands for improving the corrosion resistance of galvanized steel sheets, it is known that the corrosion resistance can be improved by increasing the amount of zinc plating (adhesion amount). Many methods have been proposed. Many of these are
It contains iron group elements such as Fe, Ni, and Co as alloying components. These zinc-iron group electroplated steel sheets are characterized by excellent corrosion resistance unpainted or after painting, as seen in Japanese Patent Publication No. 50-29821 and Japanese Patent Publication No. 57-61831, and are used industrially. Although it has been produced and put into practical use, it is strongly desired to further improve its corrosion resistance. As an electroplated steel sheet containing Cr during Zn or Zn-based alloy plating, for example,
and Publication No. 59-40234, JP-A-61-130498, 61-
270398, 62-54099, etc. are disclosed. In all of these, the content of Cr is as small as 5% or less, and the effect of Cr on corrosion resistance can only be incidental. Therefore, for the purpose of improving corrosion resistance, it is strongly desired to eutectoid a higher content of Cr. (Problem to be solved by the invention) However, conventionally, Zn-
There was no Cr electroplating technology. In other words, simply increasing the concentration of trivalent Cr ions in the plating bath does not result in a plating with good workability, and there are problems such as a sudden decrease in current efficiency, making it difficult to industrially use electroplating with a high Cr content. It was extremely difficult to obtain steel plates. In view of the above problems, the present invention provides an unprecedented high
The object of the present invention is to provide a highly practical composite electroplated steel sheet with a Cr content that has excellent corrosion resistance and workability. (Means for Solving the Problem) The present invention introduces a water-soluble cationic polymer into a plating bath containing Zn 2+ and Cr 3+ , and by this action,
Unprecedented high Cr by promoting Cr precipitation
We were able to obtain a high content rate and also succeeded in securing processability by eutectoiding a small amount of cationic polymer. The gist of the present invention is as follows: [1] A water-soluble cationic polymer consisting of a polymer of quaternary amine with a molecular weight of 10 3 to 10 6 with 5 to 30% Cr added to a plating solution is electrically applied to the surface of a steel sheet. A cationic polymer that is precipitated in
A composite electroplated steel sheet with excellent corrosion resistance, characterized by forming a composite electroplated layer containing 0.005 to 5% by weight and the balance being Zn. [2] A cationic product made by electrically depositing a water-soluble cationic polymer consisting of a polymer of 5 to 30% by weight of Cr and a quaternary amine with a molecular weight of 10 3 to 10 6 added to a plating solution on the surface of a steel plate. polymer
A composite electroplated layer with excellent corrosion resistance characterized by forming a composite electroplated layer containing 0.005 to 5% by weight, the balance being Zn, and forming a Zn or Zn-based alloy plating layer as an upper layer of the composite electroplated layer. Plated steel plate. It is. (Function) The corrosion resistance of the composite electroplated steel sheet of the present invention is mainly a function of Cr. The Cr content is preferably 5 to 30% by weight. If it is less than 5% by weight, some effect is observed, but there remains a tendency for red rust to occur and corrosion resistance is not sufficient. When the amount is 5% by weight or more, the occurrence of red rust is suppressed in, for example, a salt spray test, and an epoch-making effect appears. Such high corrosion resistance cannot be achieved by conventionally known Zn plating or alloy plating such as Zn-Fe or Zn-Ni. When Cr coexists with Zn, it does not become passivated, and together with Zn it participates in the sacrificial anticorrosion effect, and the corrosion products of Cr deposit a poorly soluble protective film on the corroded areas, thereby suppressing corrosion. This is thought to be the reason why it exhibits high corrosion resistance. When the Cr content exceeds 30% by weight, corrosion resistance is good, but even with the eutectoid effect of the cationic polymer described below, deterioration of so-called powdering property, in which the plating layer peels off during processing such as press processing, is prevented. This is difficult to apply in practice. Cationic polymer is a precipitation accelerator for Cr,
In addition, by eutectoiding a small amount of Cr in the plating layer, it improves powdering resistance during processing.
Such eutectoid effect of cationic polymers is due to Cr
Ions inhibit the uniform deposition growth of Zn, resulting in uniformity and
It is presumed that the purpose is to prevent a flickering structure lacking in smoothness. That is, through the eutectoid cationic polymer, Zn and
The content of the cationic polymer is preferably 0.005 to 5% by weight, which is considered to form a dense plating layer in which Cr is uniformly mixed or alloyed. If the content is less than 0.005% by weight, the effect on powdering resistance during processing is poor, and if the content exceeds 5% by weight, it is not only difficult to obtain even if the concentration of cationic polymer in the plating bath is increased, but also a large amount If eutectoid is used, it will cause a decrease in plating adhesion. From the viewpoint of processability, it is sufficient if the cationic polymer is eutectoid at a content of 1/1000 or more of the Cr content. The water-soluble cationic polymer used in the present invention is 4
Polymers of grade amines are effective polymers, the molecular weight being preferably between 10 3 and 10 6 in this case. Among the following amine polymers, polyamine sulfone (abbreviated as PAS) and polyamine (PA) are Cr
Most effective as a precipitation promoter. It is thought that the adsorption effect of the amine group and the bonding of metal ions or metals with the sulfone group are contributing factors. Basically, the following quaternary amine salts (ammonium salts)
【式】を主鎖に含むホモ
ポリマーあるいはコポリマーで構成されている。
以下具体的にいくつかの化合物を列挙する。
ジアリルアミンから得られる高分子があげられ
る。R1，R2は低級アルキル基を示し、
It is composed of a homopolymer or copolymer containing [Formula] in the main chain. Some compounds will be specifically listed below. Examples include polymers obtained from diallylamine. R 1 and R 2 represent lower alkyl groups,
【式】と略す。Abbreviated as [formula].
【式】と略す。
ＸはCl-，HSO4 -，H2PO4 -，Ｒ−SO3 -（Ｒは
C1〜C4のアルキル基）、NO3 -のアニオンを示す。
あるいはビニルベンジルから合成される高分子
があげられる。R1，R2，R3は炭化水素を示し、
Abbreviated as [formula]. X is Cl - , HSO 4 - , H 2 PO 4 - , R-SO 3 - (R is
C 1 -C 4 alkyl group), NO 3 - anion. Another example is a polymer synthesized from vinylbenzyl. R 1 , R 2 , R 3 represent hydrocarbons,
【式】と略
ＸはCl-，HSO4 -，H2PO4 -，Ｒ−SO3 -，NO3
−、のアニオンを示す。
あるいはアリルアミンポリマーがあげられる。[Formula] and abbreviation X is Cl - , HSO 4 - , H 2 PO 4 - , R-SO 3 - , NO 3
- indicates an anion. Alternatively, allylamine polymer can be mentioned.
【式】と略す。
R1，R2，R3は炭化水素を示し、ＸはCl-，
HSO4 -，H2PO4 -，Ｒ−SO3 -，NO3 -のアニオン
を示す。Rn＝CnH2o+1（ｎ＝１，２，３）であ
る。
この他１，２，３級アミンのポリマーも前述の
４級アミンポリマーに及ばないがCr析出促進剤
として効果がある。
めつき付着量は、10〜50ｇ／m2で十分耐食性を
確保できる。また、Zn，Cr、カチオンポリマー
以外にも、Fe，Ni，Co，Pb，Sn，Ag，In，Bi，
Cu，Sb，Ag，Al，Ti，Na，Ｐ，Ｓ等が不可避
的に微量共析していても、本質的に本発明の効果
は変わらない。
なお、本発明のめつき層としては、均一単相と
する場合だけでなく、上記めつき層組成を有する
範囲において、めつき層内に分散または層状的に
構成したものや、深さ方向に濃度勾配を有するも
のなども単相と同様に良好な性能を発揮するの
で、本発明の範囲に含むこととする。
このようにしてなる複合電気めつき鋼板は、単
層のままでもよいし、上層にZnもしくはZn−
Ni，Zn−Fe等のZn系合金めつきを少量施しても
よい。上層に、ZnもしくはZn系合金めつきを施
す場合には、１〜５ｇ／m2が望ましく、こうする
ことにより、塩水噴霧試験のような湿潤環境下で
の塗装後耐食性が更に向上する。
次に、本発明の複合電気めつき鋼板の製造方法
であるが、Zn2+イオン、Cr3+イオン及び、PAS
の如き４級アミンの重合物等の水溶性カチオンポ
リマーを0.01〜20ｇ／含む、PH0.5〜３の浴温
40〜70℃の酸性めつき浴を用いて20A／ｄm2以上
の電気めつきすればよい。めつき浴中には必要に
応じて、SiO2，TiO2，Al2O3等の酸化物粒子を
添加してもよい。更に、Na+、K+，NH4 +イオン
等の塩を添加することは、浴の電導度を高めるた
めに有効である。上層のZnもしくはZn系合金め
つきは、周知の電気めつき法を適用することがで
きる。その場合、下層めつき浴から持ち出される
Crイオンやカチオンポリマーを含むドラツグア
ウトを、上層めつき前に水洗により十分除去する
ことが好ましい。
本発明の構造は必ずしも鋼板面の両面に対して
用いる必要はなく、用途に応じて片方のみに適用
し、他の面は鋼板面のまま、もしくは他のめつき
層、あるいは有機皮膜を被覆しためつき層として
もよい。
本発明を適用する素地鋼板は通常ダル仕上げ圧
延をした軟鋼板であるが、ブライト仕上げ圧延を
した軟鋼板、鋼成分としてMn，Ｓ，Ｐ等を多く
含んだ鋼板張力鋼板、Cr，Cu，Ni，Ｐ等を多く
含んだ腐食速度の小さい高耐食性鋼板でも適用可
能である。
（実施例）
冷延鋼板を、アルカリ脱脂し、５％硫酸で酸洗
した後、水洗し、以下の条件により、電気めつき
を行なつた。ポンプ攪拌により液流速90m／
min、極間距離10mmとし、浴温60℃、PH２の硫酸
酸性浴を用いた。めつき浴組成はZn2+イオン70
ｇ／、Cr3+イオン１〜30ｇ／、カチオンポリ
マー（分子量１万のポリアミンポリマー（PA））、
あるいは分子量12万のポリアミンスルホンポリマ
ー（PAS））0.01〜20ｇ／、Na+イオン16ｇ／
とし、Cr及びカチオンポリマーの含有率は、
それぞれの添加量及び電流密度によりコントロー
ルし、めつき付着量は20ｇ／m2とした。また、１
部については上層に、周知の条件でZnもしくは
Zn系合金めつきを３ｇ／m2施した。
このようにして製造した複合電気めつき鋼板の
めつき組成及び耐食性、加工性評価結果を第１表
に示す。なお、めつき層中のZn，Crについては
原子吸光法で分析し、カチオンポリマーについて
は、燃焼法によりＣ分析を行ないカチオンポリマ
ー量に換算した。耐食性、加工性評価方法につい
ては以下の通りである。
(1) 未塗装耐食性
塩水噴霧試験（JIS Z2371に順拠、SSTと
略）672時間後の赤錆発生面積で評価した。
１％以下 ：◎
１％超〜10％以下 ：○
10％超〜30％以下 ：△
30％超 ：×
サイクル腐食試験（CCTと略）
上記サイクルを１サイクルとし、30サイクル後
の板厚減少量で評価した。
0.1mm以下 ：◎
0.1mm超〜0.2mm以下 ：○
0.2mm超〜0.3mm以下 ：△
0.3mm超 ：×
(2) 塗装後耐食性
浸漬型リン酸塩処理、カチオン電着塗装20μm
を施こし、中塗り、水研ぎ、上塗り塗装をして総
合塗膜厚100μmとし、地鉄に達するクロスカツト
を入れた試験片について、SSTを1000時間及び
上記サイクルのCCTを60サイクル行ないそれぞ
れについてクロスカツト部のふくれ巾で評価し
た。
１mm以下 ：◎
超〜３mm以下 ：○
３mm超〜５mm以下 ：△
５mm超 ：×
(3) 加工性
50φ×25Hの円筒プレス成形を行なつた後、加
工面についてテープ剥離を行ない、重量減少量で
評価した。
２mg以下 ：◎
２mg超〜５mg以下 ：○
５mg超〜８mg以下 ：△
８mg超 ：×
本発明例である実施例は、比較例に比して、耐
食性、加工性共に明らかに良好である。Abbreviated as [formula]. R 1 , R 2 , R 3 represent hydrocarbons, X represents Cl - ,
Indicates anions of HSO 4 - , H 2 PO 4 - , R-SO 3 - , and NO 3 - . Rn=CnH2 o+1 (n=1, 2, 3). In addition, polymers of primary, secondary, and tertiary amines are also effective as Cr precipitation promoters, although they are not as effective as the above-mentioned quaternary amine polymers. The amount of plating deposited is 10 to 50 g/m 2 to ensure sufficient corrosion resistance. In addition to Zn, Cr, and cationic polymers, we also offer Fe, Ni, Co, Pb, Sn, Ag, In, Bi,
Even if a small amount of Cu, Sb, Ag, Al, Ti, Na, P, S, etc. inevitably eutectoid, the effect of the present invention does not essentially change. In addition, the plating layer of the present invention is not limited to a uniform single-phase plating layer, and may be dispersed or layered within the plating layer within the range having the above-mentioned plating layer composition, or may be structured in a layered manner in the depth direction. Those having a concentration gradient exhibit good performance as well as a single phase, and therefore are included in the scope of the present invention. The composite electroplated steel sheet formed in this way may be left as a single layer, or may have Zn or Zn-
A small amount of Zn-based alloy plating such as Ni or Zn-Fe may be applied. When the upper layer is plated with Zn or a Zn-based alloy, the plating is preferably 1 to 5 g/m 2 , and this further improves the corrosion resistance after coating in a humid environment such as a salt spray test. Next, in the method for manufacturing a composite electroplated steel sheet of the present invention, Zn 2+ ions, Cr 3+ ions, and PAS
Contains 0.01 to 20 g of a water-soluble cationic polymer such as a quaternary amine polymer, and has a bath temperature of PH 0.5 to 3.
Electroplating may be carried out at 20 A/dm 2 or more using an acidic plating bath at 40 to 70°C. If necessary, oxide particles such as SiO 2 , TiO 2 , Al 2 O 3 and the like may be added to the plating bath. Furthermore, addition of salts such as Na + , K + , NH 4 + ions is effective in increasing the conductivity of the bath. For plating the upper layer with Zn or Zn-based alloy, a well-known electroplating method can be applied. In that case, it will be removed from the lower layer plating bath.
It is preferable to thoroughly remove dragout containing Cr ions and cationic polymers by washing with water before plating the upper layer. The structure of the present invention does not necessarily have to be applied to both sides of the steel plate, but can be applied to only one side depending on the application, and the other side can be left as the steel plate or coated with another plating layer or an organic film. It may also be used as a storage layer. The base steel plate to which the present invention is applied is usually a mild steel plate that has been subjected to dull finish rolling, but it can also be a mild steel plate that has been brightly finished rolled, a steel plate containing a large amount of Mn, S, P, etc. as a steel component, a tensile steel plate, a steel plate containing a large amount of Mn, S, P, etc. as steel components, Cr, Cu, Ni. , P, etc., and has a low corrosion rate, it can also be applied to highly corrosion-resistant steel sheets. (Example) A cold rolled steel sheet was degreased with alkali, pickled with 5% sulfuric acid, washed with water, and electroplated under the following conditions. Liquid flow rate 90m/by pump stirring
The distance between the electrodes was 10 mm, and a sulfuric acid acid bath with a bath temperature of 60° C. and a pH of 2 was used. Plating bath composition is Zn 2+ ion 70
g/, Cr 3+ ions 1 to 30 g/, cationic polymer (polyamine polymer (PA) with a molecular weight of 10,000),
Or polyamine sulfone polymer (PAS) with a molecular weight of 120,000) 0.01 to 20g/, Na + ion 16g/
The content of Cr and cationic polymer is
The amount of plating deposited was 20 g/m 2 by controlling each additive amount and current density. Also, 1
For the upper layer, Zn or
Zn-based alloy plating was applied at 3 g/m 2 . Table 1 shows the plating composition, corrosion resistance, and workability evaluation results of the composite electroplated steel sheet produced in this manner. Incidentally, Zn and Cr in the plating layer were analyzed by atomic absorption spectrometry, and the cationic polymer was analyzed by C analysis by the combustion method and converted into the amount of cationic polymer. The corrosion resistance and workability evaluation methods are as follows. (1) Unpainted corrosion resistance Evaluated by the area of red rust after 672 hours of salt spray test (according to JIS Z2371, abbreviated as SST). 1% or less: ◎ More than 1% to less than 10%: ○ More than 10% to less than 30%: △ More than 30%: × Cycle corrosion test (abbreviated as CCT) The above cycle was considered as one cycle, and evaluation was made based on the amount of reduction in plate thickness after 30 cycles. 0.1mm or less: ◎ More than 0.1mm to 0.2mm or less: ○ More than 0.2mm to 0.3mm or less: △ More than 0.3mm: × (2) Corrosion resistance after painting Immersion phosphate treatment, cationic electrodeposition coating 20μm
The test pieces were subjected to intermediate coating, wet sanding, and top coating to give a total coating thickness of 100 μm, and crosscuts reaching the base steel were subjected to SST for 1000 hours and CCT of the above cycle for 60 cycles, and crosscuts were performed for each. Evaluation was made based on the bulge width of the part. 1 mm or less: ◎ More than 3 mm or less: ○ More than 3 mm - 5 mm or less: △ More than 5 mm: × (3) Workability After performing cylindrical press molding of 50φ It was evaluated by 2 mg or less: ◎ More than 2 mg to 5 mg or less: ○ More than 5 mg to 8 mg or less: △ More than 8 mg: × The example, which is an example of the present invention, is clearly better in both corrosion resistance and workability than the comparative example.
【表】
（発明の効果）
以上述べたように、本発明はカチオンポリマー
の利用により、従来極めて困難であつたZnをベ
ースとした高Cr含有率の複合電気めつき鋼板を
達成し得たものであり、Crの作用により高耐食
性を発現するのみならず、カチオンポリマーの作
用により良好な加工性を有するので、自動車、家
電、建材用途等の防錆鋼板として好適である。[Table] (Effects of the invention) As described above, the present invention has achieved a composite electroplated steel sheet with a high Cr content based on Zn, which was extremely difficult to achieve in the past, by using a cationic polymer. It not only exhibits high corrosion resistance due to the action of Cr, but also has good workability due to the action of the cationic polymer, so it is suitable as a rust-preventing steel sheet for use in automobiles, home appliances, building materials, etc.
Claims (1)
液に添加した分子量103〜106の４級アミンの重合
物からなる水溶性カチオンポリマーを電気的に析
出せしめてなるカチオンポリマーを0.005〜５重
量％、残部Znとする複合電気めつき層を形成し
たことを特徴とする耐食性に優れた複合電気めつ
き鋼板。 ２ 鋼板の表面に、Crを５〜30重量％、めつき
液に添加した分子量103〜106の４級アミンの重合
物からなる水溶性カチオンポリマーを電気的に析
出せしめてなるカチオンポリマーを0.005〜５重
量％、残部Znとする複合電気めつき層を形成し、
該複合電気めつき層の上層としてZnもしくはZn
系合金めつき層を形成したことを特徴とする耐食
性に優れた複合電気めつき鋼板。[Claims] 1. A water-soluble cationic polymer consisting of a polymer of 5 to 30% by weight of Cr and a quaternary amine with a molecular weight of 10 3 to 10 6 added to a plating solution is electrically deposited on the surface of a steel plate. 1. A composite electroplated steel sheet with excellent corrosion resistance, characterized by forming a composite electroplated layer containing 0.005 to 5% by weight of a cationic polymer consisting of a cationic polymer, and the balance being Zn. 2 A cationic polymer made by electrolytically depositing a water-soluble cationic polymer consisting of a polymer of quaternary amine with a molecular weight of 10 3 to 10 6 with 5 to 30% by weight of Cr added to a plating solution on the surface of a steel plate. Forming a composite electroplated layer containing 0.005 to 5% by weight and the balance being Zn,
Zn or Zn as the upper layer of the composite electroplated layer
Composite electroplated steel sheet with excellent corrosion resistance, characterized by the formation of a plating layer made of an alloy.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63118118A JPH01290797A (en) | 1988-05-17 | 1988-05-17 | Composite electroplated steel sheet having superior corrosion resistance |
| CA000599581A CA1337555C (en) | 1988-05-17 | 1989-05-12 | Coated steel sheets and process for producing the same |
| EP89108750A EP0342585B1 (en) | 1988-05-17 | 1989-05-16 | Coated steel sheets and process for producing the same |
| DE89108750T DE68908471T2 (en) | 1988-05-17 | 1989-05-16 | Coated steel sheets and process for their manufacture. |
| US07/642,541 US5188905A (en) | 1988-05-17 | 1991-01-17 | Coated steel sheets |
| US07/901,033 US5242572A (en) | 1988-05-17 | 1992-06-19 | Coated steel sheets and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63118118A JPH01290797A (en) | 1988-05-17 | 1988-05-17 | Composite electroplated steel sheet having superior corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01290797A JPH01290797A (en) | 1989-11-22 |
| JPH0512439B2 true JPH0512439B2 (en) | 1993-02-18 |
Family
ID=14728478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63118118A Granted JPH01290797A (en) | 1988-05-17 | 1988-05-17 | Composite electroplated steel sheet having superior corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01290797A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0672317B2 (en) * | 1989-11-24 | 1994-09-14 | 新日本製鐵株式会社 | Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treatment and method for producing the same |
| JPH03191098A (en) * | 1989-12-19 | 1991-08-21 | Nippon Steel Corp | Production of composite electroplated steel sheet |
| JPH03191096A (en) * | 1989-12-19 | 1991-08-21 | Nippon Steel Corp | Composite electroplated steel sheet |
| JPH04224691A (en) * | 1990-12-26 | 1992-08-13 | Nippon Steel Corp | Production of highly corrosion resistant electroplated steel sheet |
Citations (10)
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|---|---|---|---|---|
| JPS5414622A (en) * | 1977-07-06 | 1979-02-03 | Hitachi Denshi Ltd | Display method for white balance |
| JPS564158A (en) * | 1979-06-22 | 1981-01-17 | Canon Inc | Copying machine |
| JPS5939515A (en) * | 1982-08-31 | 1984-03-03 | Sumitomo Heavy Ind Ltd | Manufacture of laminated web |
| JPS60211096A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
| JPS61143590A (en) * | 1984-12-15 | 1986-07-01 | Okayama Pref Gov | Production of galvanized steel material for adhesive base |
| JPS61213400A (en) * | 1985-03-15 | 1986-09-22 | Dainippon Toryo Co Ltd | Production of electroplated steel sheet |
| JPS626758A (en) * | 1985-07-03 | 1987-01-13 | Honda Motor Co Ltd | Member made of carbon fiber reinforced magnesium alloy |
| JPS6314890A (en) * | 1986-07-05 | 1988-01-22 | Nippon Steel Corp | Decorative galvanized steel sheet and its production |
| JPS63103099A (en) * | 1986-10-17 | 1988-05-07 | Kao Corp | Organic polymer composite zinc and zinc alloy plated film and production thereof |
| JPS63128193A (en) * | 1986-11-17 | 1988-05-31 | Kao Corp | Additive for electroplating bath |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5368631A (en) * | 1976-12-02 | 1978-06-19 | Kawasaki Steel Co | Znnal complex plating coated steel plate |
| JPS60125395A (en) * | 1983-12-09 | 1985-07-04 | Kawasaki Steel Corp | Zn-alumina composite electroplated steel sheet having high corrosion resistance |
-
1988
- 1988-05-17 JP JP63118118A patent/JPH01290797A/en active Granted
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414622A (en) * | 1977-07-06 | 1979-02-03 | Hitachi Denshi Ltd | Display method for white balance |
| JPS564158A (en) * | 1979-06-22 | 1981-01-17 | Canon Inc | Copying machine |
| JPS5939515A (en) * | 1982-08-31 | 1984-03-03 | Sumitomo Heavy Ind Ltd | Manufacture of laminated web |
| JPS60211096A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
| JPS61143590A (en) * | 1984-12-15 | 1986-07-01 | Okayama Pref Gov | Production of galvanized steel material for adhesive base |
| JPS61213400A (en) * | 1985-03-15 | 1986-09-22 | Dainippon Toryo Co Ltd | Production of electroplated steel sheet |
| JPS626758A (en) * | 1985-07-03 | 1987-01-13 | Honda Motor Co Ltd | Member made of carbon fiber reinforced magnesium alloy |
| JPS6314890A (en) * | 1986-07-05 | 1988-01-22 | Nippon Steel Corp | Decorative galvanized steel sheet and its production |
| JPS63103099A (en) * | 1986-10-17 | 1988-05-07 | Kao Corp | Organic polymer composite zinc and zinc alloy plated film and production thereof |
| JPS63128193A (en) * | 1986-11-17 | 1988-05-31 | Kao Corp | Additive for electroplating bath |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01290797A (en) | 1989-11-22 |
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