JPH01290797A - Composite electroplated steel sheet having superior corrosion resistance - Google Patents
Composite electroplated steel sheet having superior corrosion resistanceInfo
- Publication number
- JPH01290797A JPH01290797A JP63118118A JP11811888A JPH01290797A JP H01290797 A JPH01290797 A JP H01290797A JP 63118118 A JP63118118 A JP 63118118A JP 11811888 A JP11811888 A JP 11811888A JP H01290797 A JPH01290797 A JP H01290797A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- corrosion resistance
- cationic polymer
- composite
- layer
- 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.)
- Granted
Links
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 34
- 239000010959 steel Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 32
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 238000009713 electroplating Methods 0.000 claims abstract description 10
- 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 2
- 150000001412 amines Chemical class 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical group CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 24
- 239000011701 zinc Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 6
- -1 amine salts Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 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
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910007567 Zn-Ni Inorganic materials 0.000 description 2
- 229910007614 Zn—Ni Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 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
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005238 degreasing Methods 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
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 229910052748 manganese Inorganic materials 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
- 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
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-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
- 238000005554 pickling Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 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
- 239000000126 substance Substances 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 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っき鋼板に関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a rust-preventive composite electroplated steel sheet with excellent corrosion resistance and workability for use in automobiles, home appliances, building materials, etc.
（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
鉛メツキ鋼板が汎用されていることは周知である。(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.
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メツキ
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。However, in recent years, attempts have been made to use galvanized steel sheets as anti-rust 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 an increasing demand for corrosion resistance in harsh corrosive environments.
これら亜鉛メツキ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）Ｋ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
を抑制するだめの合金メツキが数多く提案されている。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 (coating amount) K. Many methods have been proposed.
これらの多くは、Ｆｅ。Many of these are Fe.
Ｎｉ、Ｃｏといった鉄族元素を合金成分として含有する
ものである。It contains iron group elements such as Ni and Co as alloy components.
これらの亜鉛−鉄族系電気めっき鋼板は、例えば特公昭
５０−２９８２１号公報、特公昭５７一６１８３１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せることが強く望まれている。These zinc-iron group electroplated steel sheets are characterized by excellent corrosion resistance either unpainted or after painting, as shown in Japanese Patent Publication No. 50-29821 and Japanese Patent Publication No. 57-61831, and are not suitable for industrial production. , has been put into practice, but
It is strongly desired to further improve corrosion resistance.
ＺｎないしＺｎ系合金めっき中にＣｒを含有させた電気
めっき鋼板として、例えば特公昭５９−３８３１３及び
５９−４０２３４号公報、特開昭６１４０９９号公報等
が開示されている。Electroplated steel sheets containing Cr in Zn or Zn-based alloy plating are disclosed, for example, in Japanese Patent Publications No. 59-38313 and No. 59-40234, and Japanese Patent Application Laid-Open No. 614099.
これらは何れもＣｒの含有率が５％以下と微量であって
、耐食性にとってＣｒの効果は付随的でしかあり得ない
。従って、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。All of these have a trace amount of Cr content of 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.
（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
気めっき技術がなかった。即ち、単にめっき浴中の３価
Ｃｒイオン濃度を高めても加工性の良いめっきが得られ
ず、電流効率も急減する等の障害があって工業的にＣｒ
含有率の高い電気めっき鋼板を得ることは極めて困難で
あった。(Problems to be Solved by the Invention) However, conventionally there has been no Zn-Cr electroplating technology capable of increasing the Cr content. In other words, simply increasing the trivalent Cr ion concentration 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, so Cr is not used industrially.
It has been extremely difficult to obtain electroplated steel sheets with a high content.
本発明は、上記問題点に鑑み、従来にない高Ｃｒ含有率
め耐食性かつ加工性に優れた実用性の高い複合電気めっ
き鋼板を提供するものである。In view of the above-mentioned problems, the present invention provides a highly practical composite electroplated steel sheet that has an unprecedented high Cr content, excellent corrosion resistance and workability.
（課題を解決するだめの手段）
本発明は、Ｚｎ２＋とＣｒ３＋を含むめっき浴に、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
促進することによシ、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７−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。(Means for Solving the Problem) The present invention introduces a water-soluble cationic polymer into a plating bath containing Zn2+ and Cr3+, and this action promotes Cr precipitation, thereby achieving an unprecedented high Cr content. can be obtained, and by eutectoiding a small amount of cationic poly7-,
It also succeeded in ensuring workability.
本発明の要旨は鋼板の表面に、Ｃｒ ５〜３０重量％、
カチオンポリマー０．００５〜５重量％、残部Ｚｎ
とする複合電気めっ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っき鋼板、及び鋼板の表面に、
下層としてＣｒ ５〜３０重量％、カチオンポリマー０
．００５〜５重量％、残部Ｚｎとする複合電気めっき層
を形成し、該複合電気めっき層の上層としてＺｎもしく
はＺｎ系合金めっ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っき鋼板である。The gist of the present invention is that 5 to 30% by weight of Cr is added to the surface of the steel plate.
Cationic polymer 0.005-5% by weight, balance Zn
A composite electroplated steel sheet with excellent corrosion resistance, which is characterized by forming a composite electroplated layer of, and on the surface of the steel sheet,
Cr 5-30% by weight as lower layer, 0 cationic polymer
．． A composite electroplated steel sheet with excellent corrosion resistance, characterized by forming a composite electroplating layer containing 005 to 5% by weight and the balance being Zn, and forming a Zn or Zn-based alloy plating layer as an upper layer of the composite electroplating layer. be.
（作用）
本発明の複合電気めっき鋼板の耐食性は、主としてＣ−
ｒの作用である。Ｃｒ含有率は、５〜３０ 重ｉ％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部、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。(Function) The corrosion resistance of the composite electroplated steel sheet of the present invention is mainly due to C-
This is the effect of r. The Cr content is preferably 5 to 30% by weight. If it is less than 5% by weight, some effect is observed, but there is 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.
このような高耐食性は、従来公知のＺｎめっきあるいは
Ｚｎ−Ｆｅ 、 Ｚｎ−Ｎｉ 等の合金めっきでは到
底達成することはできない。Such high corrosion resistance cannot be achieved by conventionally known Zn plating or alloy plating such as Zn-Fe or Zn-Ni.
ＣｒはＺｎとの共存下では不働態化せず、Ｚｎとともに
犠牲防食作用に力ロ担し、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。When Cr coexists with Zn, it does not become passivated, but together with Zn it plays a strong role in the sacrificial anticorrosion effect, and the corrosion products of Cr deposit a sparsely soluble protective film on the corroded areas, thereby inhibiting corrosion. It is thought that this is the reason why it exhibits high corrosion resistance.
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〇共析による作用をもっ
てしても、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す、実用上は
適用が難しい。When the Cr content exceeds 30% by weight, corrosion resistance is good, but even with the action of cationic polymer eutectoid described below, deterioration of so-called powdering property, in which the plating layer peels off during processing such as pressing, is prevented. However, it is difficult to apply in practice.
カチオンポリマーは、Ｃｒの析出促進剤であり、かつＣ
ｒと共に微量めっ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
っ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って、Ｚ
ｎ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。The cationic polymer is a precipitation accelerator for Cr and
By eutectoiding with r in a small amount within the plating layer, powdering resistance during processing is improved. It is presumed that the eutectoid effect of the cationic polymer is that Cr ions inhibit the uniform electrodeposited growth of Zn and prevent a flickering structure lacking in uniformity and smoothness. . That is, through the eutectoid cationic polymer, Z
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 n and Cr are uniformly mixed or alloyed.
０．００５０５重量％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
っ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、めっき密着性が低下す
る原因となる。加工性の観点からは、Ｃｒ含有率のｌ／
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。A content of 0.00505% by weight has little effect on powdering resistance during processing, and a content of more than 5% by weight 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 occurs, plating adhesion will deteriorate. From the viewpoint of workability, the Cr content l/
It is sufficient that the cationic polymer is eutectoid at a content of 1000 or more.
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シ、分子量は、この場
合、１０３〜１０６が望ましい。An effective water-soluble cationic polymer used in the present invention is a polymer of quaternary amine, and the molecular weight is preferably 103 to 106 in this case.
次に示すアミンポリマーの内、ポリアミンスルホン（Ｐ
ＡＳ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）あるいはコポリマーで構成されてい
る。Among the following amine polymers, polyamine sulfone (P
(abbreviated as AS) and polyamine (PA) are the most effective as Cr precipitation promoters. It is thought that the adsorption effect by the amine group and the bond between the sulfone group and the metal ion or metal contribute. Basically, it is composed of the following quaternary amine salts (ammonium salts) or copolymers.
以下具体的にいくつかの化合物を列挙する。Some compounds will be specifically listed below.
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、アルキル基を示し、
Ｒ，Ｒ。Examples include polymers obtained from diallylamine. R1
+ R2 represents a lower alkyl group or an alkyl group; R, R.
Ｘは（Ｊ−、Ｈ８０４−、Ｈ２ＰＯ４−、Ｒ−８Ｏ３−
（ＲはＣ，〜Ｃ。X is (J-, H804-, H2PO4-, R-8O3-
(R is C, ~C.
のアルキル基）、ＮＯ♂のアニオンを示す。(alkyl group), indicates an anion of NO♂.
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。ＲＩ ＋ Ｒ２＋ Ｒ３は炭化水素を示し、Ｒ，
Ｒ２Ｒ３
ＸはＣ４−、Ｈ８Ｏ４”−、Ｈ２ＰＯ４−、Ｒ−８Ｏ８
”−、ＮＯ３−、のアニオンを示す。Another example is a polymer synthesized from vinylbenzyl. RI + R2+ R3 represents a hydrocarbon, R,
R2R3 X is C4-, H8O4''-, H2PO4-, R-8O8
”-, NO3-, is an anion.
あるいはアリルアミンポリマーがアケラれる。Alternatively, allylamine polymer can be used.
＋ｃＨ２−ＣＨ÷ −ＰＡＲと略す。It is abbreviated as +cH2-CH÷-PAR.
Ｉｎ
ＲＩ ＋ Ｒ２＋ Ｒ３は炭化水素を示し、ＸはＣＪ−
、Ｈ３Ｏ，−。In RI + R2+ R3 represents a hydrocarbon, X is CJ-
,H3O,-.
Ｈ２ＰＯ４−、Ｒ−８Ｏ３−、Ｎｏ、−のアニオンを示
す。Indicates anion of H2PO4-, R-8O3-, No, -.
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。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.
めっき付着量は、１０〜５０２β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、 Ａｙ、
Ｉｎ。A coating weight of 10 to 502β can ensure sufficient corrosion resistance. In addition to Zn, Cr, and cationic polymers,
Fe, Ni, Co, Pb, Sn, Ay,
In.
Ｂｉ、Ｃｕ、Ｓｂ、Ａｓ、Ａｌ、Ｔｉ、？Ｊａ、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。Bi, Cu, Sb, As, Al, Ti,? Ja, P, S
Even if a small amount of these substances inevitably eutectoid, the effects of the present invention do not essentially change.
なお、本発明のめつき層としては、均−単槽と脂
する場合だけでなく、上記めっき層組成を有する範囲に
おいて、めっ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。In addition, the plating layer of the present invention is not limited to the case where the plating layer is uniformly coated in a single tank, but also the plating layer that is dispersed or structured in a layered manner within the plating layer within the range having the above plating layer composition, or the plating layer that is formed 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.
このようにしてなる複合電気めっき鋼板は、単層のまま
でもよいし、上層にＺｎもしくはＺｎ −Ｎｉ 。The composite electroplated steel sheet formed in this way may be left as a single layer, or may have Zn or Zn-Ni as an upper layer.
Ｚｎ −Ｆｅ 等のＺｎ系合金めっきを少量施しても
よい。A small amount of Zn-based alloy plating such as Zn-Fe may be applied.
上層に、ＺｎもしくはＺｎ系合金めっきを施す場合には
、１〜５ｙＡＴ？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。When applying Zn or Zn-based alloy plating to the upper layer, 1 to 5yAT? is desirable, and by doing so, the corrosion resistance after coating in a humid environment such as a salt spray test is further improved.
次に、本発明の複合電気めっ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．
０１〜２０ ？／を含む、ｐＨ０，５〜３の浴温４０〜
７０℃の酸性めっき浴を用いて２０Ａ／ｄｍ’以上で電
気めっきすればよい。めっき浴中には必要に応じて、５
ｉ０２ 、 ＴｉＯ２，Ａｌ２Ｏ２等の酸化物粒子を添
加してもよい。更に、Ｎａ 、 Ｋ 、 ＮＨ，＋
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系合金めっき
は、周知の電気めっき法を適用することができる。その
場合、下層めっ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ッグアウトを、上層めっき前に
水洗によ）十分除去することが好ましい。Next, in the method for manufacturing a composite electroplated steel sheet of the present invention, a water-soluble cationic polymer such as a polymer of Zn2+ ions, Cr3+ ions, and a quaternary amine such as PAS is added at 0.
01~20? / including pH 0.5-3 bath temperature 40-
Electroplating may be performed at 20 A/dm' or higher using an acidic plating bath at 70°C. In the plating bath, if necessary,
Oxide particles such as i02, TiO2, Al2O2, etc. may be added. Furthermore, Na, K, NH,+
Adding salts such as ions is effective in increasing the conductivity of the bath. A well-known electroplating method can be applied to the Zn or Zn-based alloy plating on the upper layer. In that case, it is preferable to sufficiently remove drag-out containing Cr ions and cationic polymers carried out from the lower layer plating bath (by washing with water before plating the upper layer).
本発明の構造は必ずしも鋼板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、池の面は鋼板
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。The structure of the present invention does not necessarily have to be applied to both sides of a steel plate, but can be applied to only one side depending on the application, and the pond surface can be left as the steel plate surface or coated with another plating layer or an organic film. It may also be used as a layer.
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、プライト仕上は圧延をした軟鋼板、鋼
成分としてＭｎ、Ｓ、Ｐ 等を多く含んだ高張力鋼板
、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。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, while the prite finish is a rolled mild steel plate, a high tensile strength steel plate that contains a large amount of Mn, S, P, etc. as steel components, Cr, Cu, It is also applicable to highly corrosion-resistant steel plates that contain a large amount of Ni, P, etc. and have a low corrosion rate.
（実施例）
冷延鋼板を、アルカリ脱脂し、５チ硫酸で酸洗した後、
水洗し、以下の条件により、電気めっきを行なった。ポ
ンプ攪拌によシ液流速９０ ｍ／ｍｉｎ、極間距離Ｌｏ
ｗとし、浴温６０℃、ｐＨ２の硫酸酸性浴を用いた。め
っき浴組成は、Ｚｎ イオン７０ｆ／Ｌ、Ｃｒ３＋イ
オン１〜３０ ？／Ｌ、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） ） ０．０
１〜２０り／’Ｌ％Ｎａ イオン１６ｙ７ｔ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、めっき付着量は２０
９／ｎｉ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系合金めっきを３ ｙＡｒ？施
した。(Example) After degreasing a cold rolled steel plate with alkali and pickling with 5-thiosulfuric acid,
After washing with water, electroplating was performed under the following conditions. Liquid flow rate 90 m/min due to pump stirring, distance between poles Lo
A sulfuric acid acidic bath with a bath temperature of 60° C. and a pH of 2 was used. The plating bath composition is Zn ion 70f/L, Cr3+ ion 1~30? /L, cationic polymer (polyamine polymer (PA) with a molecular weight of 10,000, or polyamine sulfone polymer (PAS) with a molecular weight of 120,000) 0.0
1 to 20/'L% Na ion 16y7t, Cr
The content of cationic polymer and cationic polymer was controlled by the amount added and current density, and the coating weight was 20%.
It was set as 9/ni. In addition, for one part, the upper layer was plated with Zn or Zn-based alloy under well-known conditions at 3 yAr? provided.
このようにして製造した複合電気めっき鋼板のめつき組
成及び耐食性、加工性評価結果を第１表に示す。なお、
めっき層中の加、 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。Table 1 shows the plating composition, corrosion resistance, and workability evaluation results of the composite electroplated steel sheet manufactured in this manner. In addition,
Cr in the plating layer was analyzed by atomic absorption spectrometry, and cationic polymer was analyzed by combustion method and converted into the amount of cationic polymer. The corrosion resistance and workability evaluation methods are as follows.
（１）未塗装耐食性
■塩水噴霧試験（ＪＩＳ ｚ２３７１に準拠、ＳＳＴと
略）６７２時間後の赤錆発生面積で評価した。(1) Unpainted Corrosion Resistance - Salt spray test (according to JIS z2371, abbreviated as SST) Evaluated by the area where red rust occurred after 672 hours.
１％以下： ◎
１チ超〜１０％以下： ０
１０％超〜３ｏチ以下： △
３０％超 ： ×
■サイクル腐食試験（ＯＣＴ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。1% or less: ◎ More than 1 inch to 10% or less: 0 More than 10% to 3 degrees or less: △ More than 30%: × ■Cycle corrosion test (abbreviated as OCT) The above cycle is one cycle, and the plate thickness after 30 cycles Evaluation was made based on the amount of decrease.
０．１喘以下： ◎
０．１鵡超〜０．２＋ｍ以下： ０
０．２１超〜０．３Ｉ以下： △
０．３ｍ超超：×
（２）塗装後耐食性
浸漬型リン酸塩処理、カチオン電着塗装２０μ口を施こ
し、中塗り、水研ぎ、上塗り塗装をして総合塗膜厚１０
０μｍとし、地鉄に達するクロスカットを入れた試験片
について、ＳＳＴを１０００時間及び上記サイクルのＯ
ＣＴを６０サイクル行ないそれぞれについてクロスカッ
ト部のふくれ巾で評価した。0.1 or less: ◎ More than 0.1 to 0.2+m: 0 More than 0.21 to less than 0.3I: △ More than 0.3m: × (2) Post-painting corrosion-resistant immersion phosphate treatment, Apply a cationic electrodeposition coating of 20 μm, then apply an intermediate coat, wet sanding, and top coat to achieve a total film thickness of 10
For the test piece with a crosscut reaching the base metal of 0 μm, SST was carried out for 1000 hours and the O of the above cycle was applied.
CT was performed for 60 cycles, and each time was evaluated based on the bulge width of the cross-cut portion.
１ｓ＋以下二〇
１謔超〜３＋＋＋ｍ以下： ０
３Ｍ超〜５膿以下： △
５喘超：×
（３）加工性
５０φ×２５Ｈの円面プレス成形を行なった後、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。1 s+ or less 201 yen to 3+++ m or less: 0 3 M or less to 5 pus or less: △ More than 5 pus: × (3) Workability After performing circular press molding of 50φ x 25H, tape peeling is performed on the processed surface. , evaluated by weight loss.
２ｍ９以下： ◎
２ｍ９超〜５ ｍ９以下： ０
５１ｎ９超〜８ Ｌｎ９以下： △
８ ｍ９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。2 m9 or less: ◎ More than 2 m9 to 5 m9 or less: 0 More than 51n9 to 8 Ln9 or less: △ 8 More than m9: be.
（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ったＺｎをベースとした高Ｃ
ｒ含有率の複合電気めっき鋼板を達成し得たものであシ
、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。(Effects of the Invention) As described above, the present invention utilizes a cationic polymer to produce Zn-based high C
This is a composite electroplated steel sheet with a high R content.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, making it suitable for use in automobiles, home appliances, and building materials. It is suitable as a rust-proof steel plate.
手続７市正ｐ↓ 昭和６３年６り／乙日Procedure 7 Municipality page ↓ June 1988/Otsuji
Claims (3)
リマー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。(1) A composite electroplated steel sheet with excellent corrosion resistance, characterized in that a composite electroplated layer consisting of 5 to 30% by weight of Cr, 0.005 to 5% by weight of a cationic polymer, and the balance Zn is formed on the surface of the steel sheet. .
カチオンポリマー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。(2) 5 to 30% by weight of Cr as a lower layer on the surface of the steel plate,
Corrosion resistance characterized by forming a composite electroplated layer containing 0.005 to 5% by weight of a cationic polymer and the balance being Zn, and forming a Zn or Zn-based alloy plating layer as an upper layer of the composite electroplating layer. Excellent composite electroplated steel sheet.
特許請求の範囲第１項、第２項記載の耐食性に優れた複
合電気めつき鋼板。(3) A composite electroplated steel sheet with excellent corrosion resistance according to claims 1 and 2, wherein the cationic polymer is a quaternary amine polymer.
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 true JPH01290797A (en) | 1989-11-22 |
| JPH0512439B2 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03166396A (en) * | 1989-11-24 | 1991-07-18 | Nippon Steel Corp | Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treating property and its production |
| JPH03191096A (en) * | 1989-12-19 | 1991-08-21 | Nippon Steel Corp | Composite electroplated steel sheet |
| JPH03191098A (en) * | 1989-12-19 | 1991-08-21 | Nippon Steel Corp | Production of composite electroplated steel sheet |
| JPH04224691A (en) * | 1990-12-26 | 1992-08-13 | Nippon Steel Corp | Production of highly corrosion resistant electroplated steel sheet |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5414622A (en) * | 1977-07-06 | 1979-02-03 | Hitachi Denshi Ltd | Display method for white balance |
| JPS564158B2 (en) * | 1976-12-02 | 1981-01-28 | ||
| JPS60211096A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
| JPS61213400A (en) * | 1985-03-15 | 1986-09-22 | Dainippon Toryo Co Ltd | Production of electroplated steel sheet |
| JPS626758B2 (en) * | 1983-12-09 | 1987-02-13 | Kawasaki Steel Co |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPS61143590A (en) * | 1984-12-15 | 1986-07-01 | Okayama Pref Gov | Production of galvanized steel material for adhesive base |
| JPH0620639B2 (en) * | 1985-07-03 | 1994-03-23 | 本田技研工業株式会社 | Carbon fiber reinforced magnesium alloy member |
| 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 |
-
1988
- 1988-05-17 JP JP63118118A patent/JPH01290797A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS564158B2 (en) * | 1976-12-02 | 1981-01-28 | ||
| JPS5414622A (en) * | 1977-07-06 | 1979-02-03 | Hitachi Denshi Ltd | Display method for white balance |
| JPS626758B2 (en) * | 1983-12-09 | 1987-02-13 | Kawasaki Steel Co | |
| JPS60211096A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
| JPS61213400A (en) * | 1985-03-15 | 1986-09-22 | Dainippon Toryo Co Ltd | Production of electroplated steel sheet |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03166396A (en) * | 1989-11-24 | 1991-07-18 | Nippon Steel Corp | Highly corrosion resistant composite electroplated steel sheet excellent in chemical conversion treating property and its production |
| JPH03191096A (en) * | 1989-12-19 | 1991-08-21 | Nippon Steel Corp | Composite electroplated steel sheet |
| JPH03191098A (en) * | 1989-12-19 | 1991-08-21 | Nippon Steel Corp | Production of composite electroplated steel sheet |
| JPH04224691A (en) * | 1990-12-26 | 1992-08-13 | Nippon Steel Corp | Production of highly corrosion resistant electroplated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0512439B2 (en) | 1993-02-18 |
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