JPH01176096A - Composite electroplated steel sheet having high corrosion resistance - Google Patents
Composite electroplated steel sheet having high corrosion resistanceInfo
- Publication number
- JPH01176096A JPH01176096A JP33405787A JP33405787A JPH01176096A JP H01176096 A JPH01176096 A JP H01176096A JP 33405787 A JP33405787 A JP 33405787A JP 33405787 A JP33405787 A JP 33405787A JP H01176096 A JPH01176096 A JP H01176096A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- steel sheet
- corrosion
- plating layer
- alloy
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 67
- 239000010959 steel Substances 0.000 title claims abstract description 67
- 238000005260 corrosion Methods 0.000 title claims abstract description 66
- 230000007797 corrosion Effects 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims description 44
- 238000007747 plating Methods 0.000 claims abstract description 62
- 239000010419 fine particle Substances 0.000 claims abstract description 45
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 25
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 23
- 239000010408 film Substances 0.000 claims abstract description 21
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 10
- 229910052745 lead Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract 6
- 239000011651 chromium Substances 0.000 claims description 35
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 26
- 230000002401 inhibitory effect Effects 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 229910001430 chromium ion Inorganic materials 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000001856 Ethyl cellulose Substances 0.000 abstract description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001249 ethyl cellulose Polymers 0.000 abstract description 2
- 235000019325 ethyl cellulose Nutrition 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 37
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000010422 painting Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 3
- -1 Cr3+ ions Chemical class 0.000 description 3
- 229910007567 Zn-Ni Inorganic materials 0.000 description 3
- 229910007614 Zn—Ni Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000005011 phenolic resin 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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、Ｚｎ−Ｆｅ系めっき層中に無機物又は有機物
の薄膜で被覆処理（この処理をマイクロカプセル化と呼
ぶことにする）された腐食阻止微粒子等を含有する高耐
食性電気複合めっき鋼板に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to a corrosion-resistant material whose Zn-Fe-based plating layer is coated with a thin film of an inorganic or organic material (this treatment will be referred to as microencapsulation). This invention relates to a highly corrosion-resistant electrolytic composite plated steel sheet containing inhibiting fine particles and the like.
（従来技術）
近年、北米、欧州をはじめとする冬期寒冷地においては
、道路凍結防止のため、岩塩や塩化カルシウムが散布さ
れ、自動車が使用される環境は増々厳しいものになって
いる。このような環境において、一定期間赤錆発生なし
、孔あきなしを満足する高耐食性自動車用めっき鋼板の
開発が急務である。これに対して、２つの開発の動きが
ある。(Prior Art) In recent years, in cold winter regions such as North America and Europe, rock salt and calcium chloride have been sprayed to prevent roads from freezing, and the environment in which automobiles are used has become increasingly harsh. In such an environment, there is an urgent need to develop highly corrosion-resistant plated steel sheets for automobiles that do not develop red rust or develop holes for a certain period of time. In response to this, there are two developments.
すなわち、米国、カナダのような電力コストの安価な国
での厚目付電気めっき鋼板の開発と日本のように電力コ
ストが高く溶接性、めっき加工密着性等に対するユーザ
ーの要求が厳しい国での薄目付で高耐食性な電気めっき
鋼板の開発がある。本発明は、後者に関するもので、薄
目付電気めっき鋼板は、現在までに、Ｚｎ−Ｆｅ−Ｚｎ
−Ｎｉ、Ｚｎ−Ｍｎ等亜鉛合金めっき鋼板およびＺｎ又
はＺｎ−Ｎｉ合金めっき層上にクロメート＋有機樹脂塗
装を施こした有機複層電気めっき鋼板が開発されている
。しかし、上記合金めっきおよび有機複Ｎ電気めっき鋼
板は２０〜３０ｇ／ｍ”程度の薄目付であり、現在国内
外自動車メーカーの目標の″耐外面錆５年（自動車外面
部に赤錆が５年間発生しないこと）ＩＩ Ｉｔ耐封
孔き１０年（自動車外面および内面からの孔あきが１０
年間生じないこと）″特にパ封孔あき１０年”を満足す
るまでに至っていないと言われている。そこで、最近で
は、さらに高耐食性を有するめっき鋼板として、めっき
層中に腐食阻止の性質を持った微粒子を分散共析させた
めっき鋼板いわゆる高耐食性複合めっき鋼板の製造が検
討されている。In other words, the development of thick electroplated steel sheets in countries with low electricity costs, such as the United States and Canada, and the development of thinner electroplated steel sheets in countries such as Japan, where electricity costs are high and users have strict requirements for weldability, plating adhesion, etc. In addition, electroplated steel sheets with high corrosion resistance have been developed. The present invention relates to the latter, and to date, thinly coated electroplated steel sheets have been produced using Zn-Fe-Zn.
Zinc alloy-plated steel sheets such as -Ni and Zn-Mn, and organic multilayer electroplated steel sheets in which a chromate + organic resin coating is applied on the Zn or Zn-Ni alloy plating layer have been developed. However, the above-mentioned alloy-plated and organic multi-N electroplated steel sheets have a light weight of about 20 to 30 g/m'', and currently the goal of domestic and foreign automakers is ``5-year resistance to external rust'' (red rust will occur on the exterior of the automobile for 5 years). II It is 10 years of sealing resistance (10 years of puncture resistance from the outside and inside of the car)
It is said that the condition has not yet been reached to satisfy the requirement of ``particularly, 10 years without a sealing hole''. Therefore, recently, as a plated steel plate with even higher corrosion resistance, the production of a plated steel plate, a so-called high corrosion-resistant composite plated steel plate, in which fine particles with corrosion-inhibiting properties are dispersed and eutectoid in the coating layer has been studied.
（発明の解決しようとする問題点）
複合めっき鋼板は分散共析する微粒子によってめっき層
に種々の性質を与えることが可能で、新しい機能をもつ
めっき鋼板として多く使用される傾向にある。例えば、
最近高耐食性を発揮する複合めっき鋼板が特開昭６０−
９６７８６号公報、特開昭６０−２１１０９４〜２１１
０９６号公報等多くの特許公報によって紹介されている
。(Problems to be Solved by the Invention) Composite plated steel sheets are capable of imparting various properties to the plated layer by means of dispersed and eutectoid fine particles, and are increasingly being used as plated steel sheets with new functions. for example,
Recently, composite plated steel sheets exhibiting high corrosion resistance have been developed in JP-A-60-
Publication No. 96786, JP-A-60-211094-211
It has been introduced in many patent publications such as No. 096.
特開昭６０−９６７８６号公報には、ＺｎやＺｎ−Ｎｉ
合金めっき層中に、防錆顔料（例えばＰｂＣｒ０．、
ＳｒＣｒＯ４、ＺｎＣｒ０．、 ＢａＣｒＯ４，Ｚｎ１
（ＰＯ４）ｚ等）を分散共析させた複合めっき鋼板とそ
の製造法が記されている。この複合めっき鋼板は、前記
合金めっきや有機複層電気めっきに比べて耐外面錆や射
孔あきに対してすぐれた耐食性を有するものと評価する
ことができる。しかしながら、特開昭６０−９６７８６
号公報のように難溶性クロム酸塩の防錆顔料（水溶液中
で、はとんど溶解しない）のみを含有しためっき鋼板は
、本発明者らが目標とする耐食性レベルに至っていない
。本発明者らの腐食促進試験結果を第１図に示す。ここ
で溶融亜鉛めっき（９０ｇ／ｍ２）は射孔あき１０年レ
ベルにあり、比較材として使用した。JP-A No. 60-96786 discloses Zn and Zn-Ni.
In the alloy plating layer, anti-rust pigments (for example, PbCr0.,
SrCrO4, ZnCr0. , BaCrO4,Zn1
(PO4)z, etc.) and its manufacturing method are described. This composite plated steel sheet can be evaluated as having superior corrosion resistance against external surface rust and perforation compared to the alloy plating and organic multilayer electroplating. However, JP-A-60-96786
A plated steel sheet containing only a slightly soluble chromate rust preventive pigment (which hardly dissolves in an aqueous solution) as disclosed in the above publication does not have the corrosion resistance level targeted by the present inventors. The results of the accelerated corrosion test conducted by the present inventors are shown in FIG. Here, the hot-dip galvanizing (90 g/m2) was at the level of 10 years perforation, and was used as a comparison material.
Ｚｎめっき中にＢａＣｒＯ４粒子のみを分散させた複合
めっき鋼板■は、溶融亜鉛めっき鋼板（９０ｇ／ｍ’
）■に比べ射孔あき性が劣っている。また、難溶性クロ
ム酸塩等の防錆顔料が充分に分散析出しためっき層を得
ることは困難である。この理由は本発明者らの推測によ
ると難溶性クロム酸塩等の防錆顔料は、亜鉛めっき洛中
において表面電位がほぼゼロであるため、鋼板を陰極に
して電解処理しても浴中ｚｎ２ ′″イオン優先析出し
、防錆顔料のめつき層への析出が起こり難く、その結果
、安定した耐食性を有する複合めっき鋼板が得られない
。また、特開昭６０−２１１０９５号公報には、Ｚｎ−
Ｎｉ合金めつき層中に、クロム、アルミナ（Ａ１２０．
）、シリカ（ＳｊＯＺ ）等を分散共析させた複合めっ
き鋼板が示されている。この公報では、めっき浴中のク
ロム供給源として塩化クロム（ＣｒＣＬ）を使用してい
るが、塩化クロムがめつき浴中で溶解し、Ｃｒ３＋イオ
ンを放出する。この浴中で鋼板を陰極にして電解処理す
ると、金属クロムおよび酸化クロム（Ｃｒ２０．・ｎＨ
，Ｏ）が析出し、めっき層はＺｎ−Ｎ１−Ｃｒ（＋Ｃｒ
、Ｏ，・ｎＨ，Ｏ）となり、さらに、アルミナやシリカ
を共析した複合めっき鋼板を製造する。この複合めっき
鋼板は、Ｚｎ−Ｎｉ合金めっきやＺｎ−Ｎｉ−Ｃｒ （
＋ Ｃｒ２Ｏ，・ｎＨ，Ｏ）めっき層に比べ、耐食性向
上幅は小さく第１図にＺｎ−Ｎｉ−Ｃｒ−Ａｌ２Ｏ，系
複合めっき鋼板■の腐食促進試験結果を示すように、射
孔あき１０年を満足するまでには至っていない。すなわ
ち、Ｚｎ−Ｎｘ−Ｃｒ−Ａ１２ｏｆｆ系複合めっき鋼板
も溶融亜鉛めっき鋼板（９０ｇ／＋ｍ” ）の封孔あき
性に及ばない。Composite plated steel sheet ■, in which only BaCrO4 particles are dispersed in Zn plating, is a hot-dip galvanized steel sheet (90 g/m'
)The perforation property is inferior to that of ■. Furthermore, it is difficult to obtain a plating layer in which a rust preventive pigment such as a hardly soluble chromate is sufficiently dispersed and precipitated. The reason for this is that anticorrosion pigments such as poorly soluble chromates have a surface potential of almost zero during galvanizing, so even if electrolytic treatment is performed using a steel plate as the cathode, the zinc2' ``Preferential precipitation of ions and precipitation of anti-rust pigments onto the plating layer are difficult to occur, and as a result, composite plated steel sheets with stable corrosion resistance cannot be obtained. −
Chromium and alumina (A120.
), silica (SjOZ), and the like are dispersed and eutectoid. This publication uses chromium chloride (CrCL) as a chromium source in the plating bath, but chromium chloride dissolves in the plating bath and releases Cr3+ ions. When electrolytically treated in this bath using a steel plate as a cathode, metallic chromium and chromium oxide (Cr20.・nH
, O) is precipitated, and the plating layer is Zn-N1-Cr(+Cr
, O, ·nH, O), and a composite plated steel sheet with alumina and silica eutectoid is manufactured. This composite plated steel sheet has Zn-Ni alloy plating and Zn-Ni-Cr (
+ Cr2O, ・nH, O) The improvement in corrosion resistance is small compared to the plated layer. We have not yet reached the point where we are satisfied with the above. That is, the Zn-Nx-Cr-A12off-based composite plated steel sheet is also inferior to the pore-sealing property of the hot-dip galvanized steel sheet (90 g/+m'').
第１図は本発明複合めっき鋼板および比較材の無塗装材
の複合腐食試験５０サイクル実施後の腐食深さ結果を示
す。FIG. 1 shows the corrosion depth results after 50 cycles of the composite corrosion test of the composite plated steel sheet of the present invention and the uncoated comparative material.
（注）複合腐食試験サイクル内容は
注 評価サンプル
１ ： Ｚｎ−０，３％ＢａＣｒＯ４複合めっき鋼板（
特開昭６０−９６７８６号公報条件にてめっき）２ ：
Ｚｎ−１％Ｎｉ−１％Ｃｒ−１％Ａｌ２Ｏ，複合めっ
き鋼板（特開昭６０−２１１０９５号公報条件にてめっ
き）３ ： Ｚｎ−１０％Ｃ０−４％ＢａＣｒ０． （
Ｓｉｎ、薄膜コート）（本発明による複合めっき）
４：溶融亜鉛厚めつき（９０ｇ／ｍ２）（問題点を解決
するための手段）
そこで、本発明者らは、より高耐食性を有する複合めっ
き鋼板開発の必要性を痛感し、鋭意検討した結果、第１
図に示すように、極薄膜で表面被覆することによりマイ
クロカプセル化された微粒子を分散共析させためっき層
を施しためっき鋼板■は、自動車用防錆鋼板としてすぐ
れた特性を有し、特に耐錆性、封孔あき性にすぐれてい
ることを見い出した。(Note) Please note the contents of the composite corrosion test cycle.Evaluation sample 1: Zn-0,3%BaCrO4 composite plated steel plate (
Plating under the conditions disclosed in JP-A No. 60-96786) 2:
Zn-1%Ni-1%Cr-1%Al2O, composite plated steel sheet (plated under the conditions disclosed in JP-A-60-211095) 3: Zn-10%C0-4%BaCr0. (
Sin, thin film coating) (composite plating according to the present invention) 4: Thick galvanizing (90 g/m2) (means for solving the problem) Therefore, the present inventors developed a composite plated steel sheet with higher corrosion resistance. After keenly realizing the necessity of
As shown in the figure, plated steel sheet■, which has a plated layer in which micro-encapsulated fine particles are dispersed and co-deposited by coating the surface with an ultra-thin film, has excellent properties as a rust-preventing steel sheet for automobiles. It was discovered that it has excellent rust resistance and pore sealing properties.
すなわち本発明の要旨は、
（１）鋼板の片面又は両面に無機物又は有機物の極薄膜
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＨｎ、 Ｃｒ、 Ｓｎ、 Ｓｂ、 Ｐｂ、 Ｍｏの
１種又は２種以上を含有するＺｎ−Ｆｅ合金のめっき層
を有してなることを特徴とする高耐食性電気複合めっき
鋼板。That is, the gist of the present invention is as follows: (1) A Zn-Fe alloy or one of Hn, Cr, Sn, Sb, Pb, Mo containing corrosion-inhibiting fine particles coated on one or both sides of a steel plate with an extremely thin film of an inorganic or organic substance. A highly corrosion-resistant electrolytic composite plated steel sheet comprising a plating layer of a Zn-Fe alloy containing one or more Zn-Fe alloys.
（２）鋼板の片面又は両面に無機物又は有機物の極薄膜
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＨｎ、 Ｃｒ、 Ｓｎ、 Ｓｂ、 Ｐｂ、 Ｍｏの
１種又は２種以上を含有するＺｎ−Ｆｅ合金のめっき層
と、その上にＺｎ、 Ｆｅ、 Ｃｏ、Ｎｉ、 Ｈｎ、
Ｃｒの１種又は２種以上からなる電気めっき層を有して
なることを特徴とする高耐食性電気複合めっき鋼板。(2) Zn-Fe alloy containing corrosion-inhibiting fine particles coated with an ultra-thin film of inorganic or organic material on one or both sides of the steel plate, or containing one or more of Hn, Cr, Sn, Sb, Pb, and Mo. Zn-Fe alloy plating layer with Zn, Fe, Co, Ni, Hn,
A highly corrosion-resistant electro-composite plated steel sheet comprising an electroplated layer consisting of one or more types of Cr.
（３）鋼板の片面又は両面に無機物又は有機物の極薄膜
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＨｎ、 Ｃｒ、 Ｓｎ、 Ｓｂ、 Ｐｂ、 Ｍｏの
１種又は２種以上を含有するＺｎ−Ｆｅ合金のめっき層
と、その上に樹脂塗装、クロメート処理後に樹脂塗装、
クロムイオンを含有する樹脂塗装の何れかの層を有して
なることを特徴とする高耐食性電気複合めっき鋼板。(3) Zn-Fe alloy containing corrosion-inhibiting fine particles coated with an ultra-thin film of inorganic or organic material on one or both sides of the steel plate, or containing one or more of Hn, Cr, Sn, Sb, Pb, and Mo. Zn-Fe alloy plating layer, resin coating on top, resin coating after chromate treatment,
A highly corrosion-resistant electro-composite plated steel sheet comprising any layer of resin coating containing chromium ions.
（４）鋼板の片面又は両面に無機物又は有機物の極薄膜
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＨｎ、 Ｃｒ、 Ｓｎ、 Ｓｂ、 Ｐｂ、 Ｍｏの
１種又は２種以上を含有するＺｎ−Ｆｅ合金のめっき層
と、その上にＺｎ、 Ｆｅ、 Ｃｏ、Ｎｉ、 Ｈｎ、
Ｃｒの１種又は２種以上からなる電気めっき層と、更に
その上に樹脂塗装、クロメート処理後に樹脂塗装、クロ
ムイオンを含有する樹脂塗装の何れかを積層してなるこ
とを特徴とする高耐食性電気複合めっき鋼板である。(4) Zn-Fe alloy containing corrosion-inhibiting fine particles coated with an ultra-thin film of inorganic or organic material on one or both sides of the steel plate, or containing one or more of Hn, Cr, Sn, Sb, Pb, and Mo. Zn-Fe alloy plating layer with Zn, Fe, Co, Ni, Hn,
High corrosion resistance characterized by an electroplated layer consisting of one or more types of Cr, and further laminated with a resin coating, a resin coating after chromate treatment, or a resin coating containing chromium ions. It is an electro-composite plated steel sheet.
（作 用） 以下本発明の複合めっき鋼板について詳細に説明する。(for production) The composite plated steel sheet of the present invention will be explained in detail below.
第２図（ａ）、（ｂ）、 （ｃ）、（ｄ）は本発明の複
合めっき鋼板モデルの断面図を示したものである。FIGS. 2(a), (b), (c), and (d) show cross-sectional views of the composite plated steel plate model of the present invention.
第２図（ａ）において、
１は鋼板で、通常の表面処理用鋼板製造工程を経て表面
清浄された薄鋼板である。In FIG. 2(a), 1 is a steel plate, which is a thin steel plate whose surface has been cleaned through a normal surface treatment steel plate manufacturing process.
２は、Ｚｎ−Ｆｅ合金めっきあるいはＺｎ−ＦｅにＨｎ
、 Ｃｒ。2 is Zn-Fe alloy plating or Hn on Zn-Fe
, Cr.
Ｓｎ、 Ｓｂ、 Ｐｂ、 Ｍｏの１種又は２種以上を混
合して含有するめっき層で、鋼板１の片面又は両面に付
着される。A plating layer containing one or a mixture of two or more of Sn, Sb, Pb, and Mo, and is attached to one or both sides of the steel plate 1.
３は、マイクロカプセル化された各種微粒子である。マ
イクロカプセル化される腐食阻止微粒子は、Ｉｌ溶性ク
ロム酸塩微粒子（ＰｂＣｒＯ，、ＢａＣｒ０．。3 is various micro-encapsulated fine particles. The microencapsulated corrosion inhibiting particulates are Il-soluble chromate particulates (PbCrO, BaCr0.
５ｒＣｒＯ，、ＺｎＣｒ０．等）、易溶性クロム酸塩（
Ｃｒｙ、、Ｎａ２Ｃｒｙ、、 Ｋ、ＣｒＯ，、Ｋ２Ｏ・
４Ｚｎｌ）４ＣｒＯ，等）、アルミ化合物（Ｚｎ−Ａ１
合金粉末、Ａ１． Ｏｌ・２ＳｉＯ２・２）１． Ｏ等
）、リン酸塩（Ｚｎ３（ＰＯ，）２・２）１２０等）、
モリブデン化合物（ＺｎＯ−ＺｎＭｏＯ４，ＣａＭｏＯ
４・ｚｎＭｏＯイＰｂＣｒＯ４・ＰｂＭｏＯ４・ｐｂｓ
ｏ４等）、チタン化合物（ＴｉＯ□・ＮｉＯ・５ｂ２ｏ
、等）をはじめとして、無機物粒子、有機物粒子例えば
弗素樹脂、ポリプロピレン樹脂のいずれでもよい。5rCrO,, ZnCr0. etc.), readily soluble chromates (
Cry, , Na2Cry, , K, CrO, , K2O・
4Znl) 4CrO, etc.), aluminum compounds (Zn-A1
Alloy powder, A1. Ol・2SiO2・2)1. O, etc.), phosphates (Zn3(PO,)2.2)120, etc.),
Molybdenum compounds (ZnO-ZnMoO4, CaMoO
4・znMoOiPbCrO4・PbMoO4・pbs
o4, etc.), titanium compounds (TiO□・NiO・5b2o
, etc.), inorganic particles, and organic particles such as fluororesin and polypropylene resin.
上記のような微粒子をマイクロカプセル化する極薄膜は
、Ｓｉｎ、、Ｔｉｅ２、Ａｌ２Ｏ３、ＺｒＯ２等の１種
又は２種以上の無機物やエチルセルロース、アミノ樹脂
、塩化ビニデン樹脂、ポリエチレン、ポリスチレン等の
有機物質から成る。その膜厚は、１０人〜１μ（望まし
くは１０人〜５００人）がよい。膜厚が１μを超えると
薄膜材質の性質が顕著に現れ（例えば５ｉｎ２では粒子
の凝集が起こりやすい）るため、めっき性がやや劣化し
、また逆に１０人より薄くなると、被覆性が劣化するた
め、粒子の溶解を抑制する効果が低下する傾向にある。The ultra-thin film that microcapsules the fine particles as described above is made of one or more inorganic substances such as Sin, Tie2, Al2O3, ZrO2, etc., or organic substances such as ethyl cellulose, amino resin, vinylidene chloride resin, polyethylene, polystyrene, etc. Become. The film thickness is preferably 10 to 1μ (preferably 10 to 500). When the film thickness exceeds 1μ, the properties of the thin film material become noticeable (for example, particles tend to aggregate easily in 5in2), so the plating performance deteriorates slightly, and conversely, when it becomes thinner than 10μ, the coating performance deteriorates. Therefore, the effect of suppressing particle dissolution tends to decrease.
微粒子をマイクロカプセル化することにより、次の作用
が発生する。上記微粒子自体は、めっき浴中で表面電位
がゼロあるいはわずかに帯電しているにすぎないため電
気泳動作用を利用する電気めっき法においては、めっき
層への充分な分散共析を確保できない。By microencapsulating fine particles, the following effects occur. Since the fine particles themselves have zero surface potential or are only slightly charged in the plating bath, sufficient dispersion and co-deposition into the plating layer cannot be ensured in an electroplating method using electrophoresis.
しかし、５ｉｎ２、Ｔｉｅ、、Ａｌ２Ｏ，、ＺｒＯ２等
の極薄膜は、それ自体電位を持っており、この性質は、
微粒子表面に被覆処理された場合でも変化することがな
いため、微粒子に電位を持たせることが可能である。こ
のため、微粒子のめっき層への分散共析量を向上させる
ことができる。However, ultrathin films such as 5in2, Tie, Al2O, ZrO2, etc. have their own potential, and this property is
Since it does not change even when the surface of the fine particles is coated, it is possible to impart a potential to the fine particles. Therefore, the amount of dispersion and eutectoid dispersion of fine particles into the plating layer can be improved.
マイクロカプセル化の２つ目の利点は、めっき浴中で微
粒子の溶解を抑制することである。例えば、難溶性クロ
ム酸塩微粒子は、微量ではあるがめつき浴に溶解し、Ｃ
ｒ’＋イオンを放出する。このＣｒ０イオンが一定濃度
以上になると、微粒子の放出量が低下したり、めっき外
観が黒く粉体状を呈し、めっき密着性も劣化する。そこ
でマイクロカプセル化によって、微粒子の溶解を抑制し
、長時間安定しためっき鋼板を得ることが可能になる。A second advantage of microencapsulation is that it suppresses dissolution of fine particles in the plating bath. For example, poorly soluble chromate fine particles dissolve in the plating bath, albeit in a small amount, and C
Release r'+ ions. When the concentration of Cr0 ions exceeds a certain level, the amount of released fine particles decreases, the appearance of the plating becomes black and powdery, and the adhesion of the plating deteriorates. Therefore, microencapsulation suppresses the dissolution of fine particles and makes it possible to obtain a plated steel sheet that is stable for a long time.
マイクロカプセル化の３つ目の利点は、微粒子のみの分
散共析よりも耐食性を向上する。その理由は、微粒子の
持つ腐食阻止性質がそのままマイクロカプセル化後も有
効に働いているためと思われる。The third advantage of microencapsulation is that it improves corrosion resistance compared to dispersion eutectoid of only fine particles. The reason for this is thought to be that the corrosion inhibiting properties of the fine particles remain effective even after microencapsulation.
分散微粒子およびマイクロカプセル化微粒子の腐食阻止
作用について詳細に述べる。The corrosion inhibiting effect of dispersed fine particles and microencapsulated fine particles will be described in detail.
微粒子をめっき層に分散共析させることにより、めっき
層の耐食性が向上する理由は、次のように考えられる。The reason why the corrosion resistance of the plating layer is improved by dispersing and eutectoiding the fine particles in the plating layer is considered to be as follows.
難溶性クロム酸塩微粒子を分散共析させた場合は、腐食
環境において、めっき層の腐食進行に伴い、分解し、Ｃ
ｒ’＋イオンを放出する。When sparingly soluble chromate fine particles are dispersed and eutectoid, they decompose as the corrosion of the plating layer progresses in a corrosive environment, and C
Release r'+ ions.
このＣｒｓ＋イオンがめつき層金属と反応して耐食性に
すぐれたクロム化合物やクロム酸化物又は水酸化物を形
成する。これにより高耐食性が向上する。These Crs+ ions react with the plating layer metal to form a chromium compound, chromium oxide, or hydroxide with excellent corrosion resistance. This improves high corrosion resistance.
さらに、このクロム化合物層が破壊されてもめっき層全
体に微粒子が均一分散していることから、再び上記形成
反応が繰り返えされ、耐食性が維持される。Furthermore, even if this chromium compound layer is destroyed, since the fine particles are uniformly dispersed throughout the plating layer, the above-mentioned formation reaction is repeated again, and corrosion resistance is maintained.
次に、マイクロカプセル化微粒子を使用した場合耐食性
が一層向上する。マイクロカプセル化によるＳｉｎ、等
の皮膜は完全密閉型でなく、多孔質となっているため、
Ｃｒ’＋イオンが少量ずつ溶出して、クロム化合物によ
る防錆皮膜を形成して耐食性を向上させることはカプセ
ル化しない微粒子の作用と同じである。しかしながら、
マイクロカプセル化した難溶性クロム酸塩微粒子の場合
、カプセル化しない難溶性クロム酸塩微粒子に比べ、Ｃ
ｒ’＋イオンの溶出速度が抑えられることにより（発明
者らの実験によると１／３〜１／１０の速度となる）、
防錆皮膜形成寿命がそれだけ延長する大きな特徴がある
。自動車向の防錆鋼板の射孔あき寿命は前述の如く１０
年という長期を目標としたものであり、実験で実施する
腐食促進試験も１％３ケ月の長期にわたるものである。Next, when microencapsulated fine particles are used, corrosion resistance is further improved. Films such as Sin, which are created by microencapsulation, are not completely sealed and are porous.
The Cr'+ ions are eluted little by little to form a rust-preventing film of chromium compounds to improve corrosion resistance, which is the same effect as that of fine particles that are not encapsulated. however,
In the case of microencapsulated sparingly soluble chromate particles, compared to non-encapsulated sparingly soluble chromate particles, C
By suppressing the elution rate of r'+ ions (according to the inventors' experiments, the rate is 1/3 to 1/10),
A major feature is that the lifespan of forming a rust-preventive film is extended accordingly. As mentioned above, the perforation life of rust-proof steel plates for automobiles is 10
The long-term goal is 2000, and the accelerated corrosion test conducted in the experiment will last for 1% and 3 months.
従って、めっき層中の分散粒子が一時的にＣｒ″＋イオ
ンを放出してクロム化合物による厚い防錆皮膜を形成す
るよりも、徐々にＣｒ”＋イオンを放出して薄い防錆皮
膜を繰り返し生成する方が、長期の防食性を発揮する。Therefore, rather than temporarily releasing Cr"+ ions and forming a thick anti-rust film made of chromium compounds, the dispersed particles in the plating layer gradually release Cr"+ ions and repeatedly form a thin anti-rust film. This will provide long-term corrosion protection.
なお、代表例として難溶性クロム酸塩微粒子から溶出す
るＣｒ’＋イオンの防食作用について述べたが、リン酸
塩化合物から溶出するＰＯ４′−イオン、モリブデン化
合物から溶出するＭ００４″−イオンについても作用は
同じである。マイクロカプセル化された微粒子の含有量
は、発明者らの実験によると、めっき付着量の０．１〜
３０ｗｔ％がよい（望ましくは０．５〜２０ｗｔ％がよ
い）。０．１％より低ければ、耐食性向上に効果が小さ
く、また３０％を超えるとめっき加工密着性が劣化する
傾向にある。As a representative example, we have described the anticorrosion effect of Cr'+ ions eluted from poorly soluble chromate fine particles, but it also acts on PO4'- ions eluted from phosphate compounds and M004''- ions eluted from molybdenum compounds. is the same.According to experiments conducted by the inventors, the content of microencapsulated fine particles is 0.1 to 0.1 to the amount of plating deposited.
The content is preferably 30 wt% (preferably 0.5 to 20 wt%). If it is less than 0.1%, the effect of improving corrosion resistance is small, and if it exceeds 30%, plating adhesion tends to deteriorate.
こうして得られた複合めっき層は、前述したように耐錆
性、謝礼あき性については充分な性能を示すが、塗装前
処理として実施する化成処理の皮膜結晶を阻害する場合
がある。例えば、マイクロカプセル化された難溶性クロ
ム酸塩微粒子を含有した複合めっき層は、カプセル化さ
れても、皮膜は完全な密閉型でなく多孔質のため微粒子
の性質を保持している。化成処理として行なわれるリン
酸塩処理はクロム上では反応しないため皮膜結晶が粗大
化したり、スケ（結晶が形成されない）を発生し、塗装
後の塗料密着性や塗装後の謝礼あきにバラツキを生ずる
要因となる。そのため、自動車外板等の塗装を施こすよ
うな場合には、第２図（ｂ）で示すように複合めっき層
上に１〜５ｇ／ｍの電気薄めっき層■を施こすことが有
効である。１ｇ／ｍより少ない場合は複合めっき層を完
全にカバーすることが難しくなり、また５ｇ／ｎ（を越
えると、めっき加工密着性がやや劣化傾向にあるため、
上記範囲でコントロールする方がよい。この電気めっき
層■は、Ｚｎ、 Ｆｅ、 Ｃｏ、 Ｈｎ、 Ｃｒの１種
又は２種以上から成るめっき層多層処理してもよい。但
しその場合の全付着量は、１〜５ｇ／蕾でコントロール
するのは前記理由と同じである。Although the composite plating layer thus obtained exhibits sufficient performance in terms of rust resistance and scratch resistance as described above, it may inhibit the film crystallization of the chemical conversion treatment performed as a pre-painting treatment. For example, a composite plating layer containing microencapsulated poorly soluble chromate fine particles retains the properties of fine particles because the film is not completely sealed and is porous even if it is encapsulated. Phosphate treatment, which is performed as a chemical conversion treatment, does not react on chromium, resulting in coarse film crystals and sagging (crystals are not formed), resulting in variations in paint adhesion and post-painting rate. It becomes a factor. Therefore, when painting automobile exterior panels, etc., it is effective to apply a thin electrolytic plating layer of 1 to 5 g/m on top of the composite plating layer, as shown in Figure 2 (b). be. If it is less than 1 g/m, it will be difficult to completely cover the composite plating layer, and if it exceeds 5 g/n, the plating adhesion will tend to deteriorate slightly.
It is better to control within the above range. This electroplating layer (1) may be multilayered with one or more of Zn, Fe, Co, Hn, and Cr. However, in that case, the total adhesion amount is controlled at 1 to 5 g/bud for the same reason as above.
また化成処理を行なわない場合は、第２図（ｃ）および
（ｄ）で示すように有機樹脂やクロメート処理後に有機
樹脂皮膜、クロムイオンを含有した有機樹脂皮膜のいず
れかの皮膜■を複合めっき層あるいは電気薄めっき層■
の上に施こすことにより、塗装後の塗料密着性や謝礼あ
き性を確保することができる。この作用は、腐食阻止微
粒子を包みこんでいるカプセルの材質が５ｉｎ２、Ｔｉ
Ｏ２等の無機物や有機物であるため、それらを含有した
複合めっき層上に処理される樹脂との結合性（−〇・・
・Ｈ等の化学結合が発生すると考えられる）が強くなる
。樹脂皮膜と塗料との密着性は良好であり、樹脂塗装を
施された複合めっき鋼板の塗料密着性も良好である。In addition, if chemical conversion treatment is not performed, as shown in Figure 2 (c) and (d), after organic resin or chromate treatment, composite plating is applied with either an organic resin film or an organic resin film containing chromium ions. layer or electroplated layer■
By applying it on top of the paint, it is possible to ensure paint adhesion and abrasion resistance after painting. This effect is due to the fact that the material of the capsule enclosing the corrosion inhibiting fine particles is 5in2, Ti.
Since they are inorganic and organic substances such as O2, their bondability with the resin treated on the composite plating layer containing them (-〇...
・It is thought that chemical bonds such as H are generated) become stronger. The adhesion between the resin film and the paint is good, and the adhesion of the resin-coated composite plated steel sheet to the paint is also good.
さらに耐食性を向上させるために、複合めっき層上にク
ロムメート処理を行なうこともよい。しかし、クロメー
ト処理のみでは自動車生産工程での脱脂、化成処理工程
においてクロメルト皮膜中のクロム（特にＣｒ’＋イオ
ン）の溶出が懸念される。Furthermore, in order to improve corrosion resistance, it is also possible to perform chromate treatment on the composite plating layer. However, with only chromate treatment, there is a concern that chromium (particularly Cr'+ ions) in the chromate film may be eluted during the degreasing and chemical conversion treatment steps in the automobile production process.
クロムの溶出は、公害衛生的に大きな社会問題となるた
め、溶出はほぼゼロに抑えなければならない。クロメー
トの手法によってクロムの溶出に差が生ずることが知ら
れている（溶出大物塗布型クロメート〉反応型クロメー
ト〉電解クロメート→溶出小）が耐食性能は溶出性の逆
の順になる。このため要求される耐食性能等に応じて使
い分けが必要となる。しかし、いずれのクロメート処理
においてもクロムの溶出が起こるため、クロメート処理
後には樹脂塗装によって被覆することが必要となる。ま
たクロムを樹脂塗料の中に含有させておいてその塗料を
鋼板上に塗装し焼き付けることでクロムを樹脂中に固定
化することで溶出防止を行なうこともできる。Since the elution of chromium is a major social problem in terms of pollution and hygiene, it is necessary to suppress the elution to almost zero. It is known that there are differences in chromium elution depending on the chromate method (large eluting coating type chromate > reactive chromate > electrolytic chromate → small eluting), but corrosion resistance performance is in the reverse order of eluting properties. Therefore, it is necessary to use them properly depending on the required corrosion resistance performance, etc. However, in any chromate treatment, chromium elution occurs, so it is necessary to cover with resin coating after the chromate treatment. It is also possible to prevent chromium from elution by incorporating chromium into a resin paint and applying the paint onto a steel plate and baking it to fix the chromium in the resin.
ここで言う有機樹脂とは、エポキシ系、エポキシフェノ
ール系、水溶性アクリルエマルジョン系樹脂等であり、
その塗装処理法は、ロールコート法、静電霧化法、カー
テンフロー法等のいずれでもよい。その時の樹脂液組成
は樹脂分が５〜５０重量％であり、またクロムを含有す
る場合はその樹脂分の１〜２０重量％のクロムイオンを
含有するものが使用される。しかし、その皮膜厚が０．
１μより少ないとクロメート中のクロムの溶出防止能が
著しく低下し、また２μを越えると溶接が難しくなるた
め、０．１〜２μの範囲でコントロールすることが望ま
しい。The organic resins mentioned here include epoxy resins, epoxy phenol resins, water-soluble acrylic emulsion resins, etc.
The coating treatment method may be any of the roll coating method, electrostatic atomization method, curtain flow method, etc. The resin liquid composition at this time has a resin content of 5 to 50% by weight, and when chromium is contained, a resin containing 1 to 20% by weight of chromium ions is used. However, the film thickness is 0.
If it is less than 1μ, the ability to prevent the elution of chromium in chromate will be significantly reduced, and if it exceeds 2μ, welding becomes difficult, so it is desirable to control it within the range of 0.1 to 2μ.
次に本発明を実施例に基づいて説明する。Next, the present invention will be explained based on examples.
冷延鋼板をアルカリ脱脂し、１０％硫酸で酸洗した後、
水洗し、以下の条件により電気複合めっきを実施した。After degreasing the cold rolled steel plate with alkali and pickling with 10% sulfuric acid,
After washing with water, electrocomposite plating was performed under the following conditions.
めっきは卓上ポンプで液循環を行ないながら、各種微粒
子のめっき浴中添加量を変化させて、浴中ｐＨ＝２の硫
酸酸性Ｚｎ−Ｆｅ系合金めっき浴中にて、鋼板を陰極と
して電解処理することにより行なった。例えば
Ｚｎ−Ｆｅ−ＢａＣｒ０４（ｓｉｏ□薄膜コート粒子）
複合めっきの場合には、
次に、複合めっきの上に行なう薄電気めっきについては
、硫酸亜鉛めっき浴中にＦｅ、 Ｃｏ、 Ｎｉ、 Ｈｎ
、Ｃｒの硫酸塩を適当量添加（Ｚｎめっきの場合は、添
加なし）しためっき浴を用いて、全付着量が１〜５ｇ／
ｍの範囲で実施した。Plating is performed by electrolytically treating the steel plate in a sulfuric acid acidic Zn-Fe alloy plating bath with a pH of 2 by changing the amount of various fine particles added to the plating bath while circulating the liquid using a tabletop pump. This was done by doing this. For example, Zn-Fe-BaCr04 (sio□ thin film coated particles)
In the case of composite plating, next, for thin electroplating performed on the composite plating, Fe, Co, Ni, Hn are added to the zinc sulfate plating bath.
, using a plating bath to which an appropriate amount of Cr sulfate was added (no addition in the case of Zn plating), the total deposition amount was 1 to 5 g/
It was carried out in the range of m.
また、樹脂塗装およびクロムを含有した樹脂塗装につい
ては、樹脂として水溶性アクリルエマルジョン系を用い
、ロールコート法により実施した。Furthermore, the resin coating and the resin coating containing chromium were carried out by a roll coating method using a water-soluble acrylic emulsion system as the resin.
また、クロメート処理樹脂塗装については、ロールコー
ト法にて樹脂塗装を行ない、クロメートについては塗布
１反応および電解のいずれのタイプでも行なった。Regarding the chromate-treated resin coating, the resin coating was performed by a roll coating method, and for chromate, both coating 1 reaction and electrolytic methods were used.
このようにして製造した種々の本発明複合めっき鋼板に
ついては、以下の性能評価試験を行なった。The following performance evaluation tests were conducted on various composite plated steel sheets of the present invention manufactured in this way.
（１）耐食性
■処理：無塗装および塗装材（Ｆｕｌｌ−ｄｉｐ型化成
処理→カチオン電着塗装→スクラッチ傷）■評価：複合
腐食試験（ＣＣＴ） ３０サイクル後の赤錆発生率と腐
食深さ測定
（注）ＣＣＴ：塩水噴＠ （３５℃ｘ ６Ｈｒ）、乾燥
（７０℃、６０％ｘ ４Ｈｒ）、湿潤（４９℃、〉９５
％Ｘ４１１ｒ）、冷凍（−２０℃Ｘ ４Ｈｒ）の順に行
い、これを１サイクルとし複合腐食試験
（２）塗料密着性
■処理： Ｆｕｌｌ−ｄｉｐ型化成処理→３コート塗装
→温水浸漬（４０℃×１０日間）
■評価：試験後２■のゴバン目×１００マスを入れ、テ
ーピングにより塗膜剥離率を測定（３）赤錆発生率の評
価は、次のように行なった。(1) Corrosion resistance ■ Treatment: Unpainted and painted materials (Full-dip type chemical conversion treatment → cationic electrodeposition coating → scratches) ■ Evaluation: Combined corrosion test (CCT) Red rust occurrence rate and corrosion depth measurement after 30 cycles ( Note) CCT: Salt water spray @ (35℃ x 6Hr), dry (70℃, 60% x 4Hr), wet (49℃, >95
Composite corrosion test (2) Paint adhesion ■ Treatment: Full-dip chemical conversion treatment → 3-coat painting → hot water immersion (40°C (10 days) ■Evaluation: After the test, 100 squares of 2■ squares were placed and the coating film peeling rate was measured by taping. (3) The rate of occurrence of red rust was evaluated as follows.
◎・・・赤錆発生率 ０％
Ｏ・・・ ／ｌ ５％以下
Δ・・・ 〃 ５〜２０％×・・・
〃 ２０〜５０％ＸＸ・・・ 〃５０％以上
（４）腐食深さの評価は次のようである。◎...Red rust occurrence rate 0% O.../l 5% or less Δ... 〃 5~20%×...
20-50% XX... 50% or more (4) Evaluation of corrosion depth is as follows.
Ｏ・・・腐食深さ ０１ＩＩｌ
ｏ・・・８０．１ｍ１１以下
Δ・・・ 〃０．１〜０．３ｍｍ
Ｘ −ｎ Ｏ，３〜０．５＋ａｍｎ・−ｎ
Ｏ，５ｍ＋ａ以上
（５）塗料密着性の評価は次のようである。O...Corrosion depth 01IIl o...80.1m11 or less Δ... 〃0.1~0.3mm X -n O,3~0.5+amn・-n
O, 5m+a or more (5) Evaluation of paint adhesion is as follows.
◎・・・塗膜剥離率 ０％
０・・・ 〃 ５％以下
Δ・・・ 〃 ５〜２０％
×・・・ 〃２０〜５０％
×ｘ・・・ １１５０％以上
第１表に評価結果を示す。これから明らかなように、本
発明の複合めっき鋼板は比較材に比べて諸性能にすぐれ
た高耐食性複合めっき鋼板であることがよくわかる。◎... Paint film peeling rate 0% 0... 〃 5% or less Δ... 〃 5-20% ×... 〃20-50% ×x... 1150% or more Evaluation results are shown in Table 1 shows. As is clear from this, it is clearly seen that the composite plated steel sheet of the present invention is a highly corrosion-resistant composite plated steel sheet that has excellent performance compared to comparative materials.
（発明の効果）
Ｓｉｎ、等の薄膜で表面被覆された腐食阻止微粒子を使
用することにより、微粒子の溶解が抑制され、また微粒
子の腐食阻止能も長期継続させることができ、非被覆粒
子分散に比べて諸性能に優れている。さらに、易溶性化
合物を表面被覆することでめっき層中への分散析出が可
能となる。本発明は、上記性質をもった微粒子を含有し
たＺｎ−Ｆｅ系合金電気複合めっき鋼板が得られる。(Effect of the invention) By using corrosion-inhibiting fine particles whose surfaces are coated with a thin film such as Sin, the dissolution of the fine particles can be suppressed, and the corrosion-inhibiting ability of the fine particles can be maintained for a long period of time. It has superior performance in comparison. Furthermore, by coating the surface with an easily soluble compound, it becomes possible to disperse and precipitate the compound into the plating layer. The present invention provides a Zn-Fe alloy electrocomposite plated steel sheet containing fine particles having the above properties.
第１図は本発明複合めっき鋼板および比較材の腐食深さ
結果を、
第２図は本発明の複合めっき鋼板モデルの断面図を示す
。
代理人 弁理士 吉 島 寧
第１図
評価サンプルFig. 1 shows the corrosion depth results of the composite plated steel sheet of the present invention and comparative materials, and Fig. 2 shows a cross-sectional view of the composite plated steel plate model of the present invention. Agent Patent Attorney Yasushi Yoshijima Diagram 1 Evaluation Sample
Claims (4)
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの１種又は２
種以上を含有するＺｎ−Ｆｅ合金のめっき層を有してな
ることを特徴とする高耐食性電気複合めっき鋼板。(1) A Zn-Fe alloy or one or two of Mn, Cr, Sn, Sb, Pb, and Mo containing corrosion-inhibiting fine particles coated with an ultrathin film of an inorganic or organic substance on one or both sides of a steel plate.
A highly corrosion-resistant electrolytic composite plated steel sheet comprising a plating layer of a Zn-Fe alloy containing at least one Zn-Fe alloy.
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの１種又は２
種以上を含有するＺｎ−Ｆｅ合金のめっき層と、その上
にＺｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｈｎ、Ｃｒの１種又は２種
以上からなる電気めっき層を有してなることを特徴とす
る高耐食性電気複合めっき鋼板。(2) Zn-Fe alloy, or one or two of Mn, Cr, Sn, Sb, Pb, and Mo, containing corrosion-inhibiting fine particles coated on one or both sides of a steel plate with an ultrathin film of an inorganic or organic substance.
It is characterized by having a plating layer of a Zn-Fe alloy containing at least one species, and an electroplating layer made of one or more of Zn, Fe, Co, Ni, Hn, and Cr on top of the plating layer. Highly corrosion resistant electro-composite plated steel sheet.
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの１種又は２
種以上を含有するＺｎ−Ｆｅ合金のめっき層と、その上
に樹脂塗装、クロメート処理後に樹脂塗装、クロムイオ
ンを含有する樹脂塗装の何れかの層を有してなることを
特徴とする高耐食性電気複合めっき鋼板。(3) Zn-Fe alloy, or one or two of Mn, Cr, Sn, Sb, Pb, and Mo, containing corrosion-inhibiting fine particles coated with an ultra-thin film of inorganic or organic material on one or both sides of the steel plate.
High corrosion resistance characterized by having a plating layer of a Zn-Fe alloy containing chromium ions or more, and on top of that a layer of resin coating, resin coating after chromate treatment, or resin coating containing chromium ions. Electro-composite plated steel sheet.
で被覆した腐食阻止微粒子を含有する、Ｚｎ−Ｆｅ合金
又はＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｈｏの１種又は２
種以上を含有するＺｎ−Ｆｅ合金のめっき層と、その上
にＺｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｍｎ、Ｃｒの１種又は２種
以上からなる電気めっき層と、更にその上に樹脂塗装、
クロメート処理後に樹脂塗装、クロムイオンを含有する
樹脂塗装の何れかを積層してなることを特徴とする高耐
食性電気複合めっき鋼板。(4) Zn-Fe alloy, or one or two of Mn, Cr, Sn, Sb, Pb, and Ho, containing corrosion-inhibiting fine particles coated with an ultra-thin film of inorganic or organic material on one or both sides of the steel plate.
a plating layer of a Zn-Fe alloy containing at least one species; an electroplating layer comprising one or more of Zn, Fe, Co, Ni, Mn, and Cr; and a resin coating thereon;
A highly corrosion-resistant electro-composite plated steel sheet characterized by being laminated with either a resin coating or a resin coating containing chromium ions after chromate treatment.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33405787A JPH01176096A (en) | 1987-12-29 | 1987-12-29 | Composite electroplated steel sheet having high corrosion resistance |
| US07/284,120 US4910095A (en) | 1987-12-29 | 1988-12-14 | High corrosion resistant plated composite steel strip |
| CA000586933A CA1334018C (en) | 1987-12-29 | 1988-12-22 | High corrosion resistant plated composite steel strip and method of producing same |
| AU27516/88A AU601094B2 (en) | 1987-12-29 | 1988-12-22 | High corrosion resistant plated composite steel strip and method of producing same |
| EP88312413A EP0323756B1 (en) | 1987-12-29 | 1988-12-29 | Corrosion-resistant plated composite steel strip and method of producing same |
| DE3851425T DE3851425T2 (en) | 1987-12-29 | 1988-12-29 | Steel sheet clad with corrosion-resistant composite material and process for its manufacture. |
| KR1019880017830A KR910007162B1 (en) | 1987-12-29 | 1988-12-29 | High corrosion resistant plated composite steel strip and method therefor |
| US07/437,439 US5082536A (en) | 1987-12-29 | 1989-11-16 | Method of producing a high corrosion resistant plated composite steel strip |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33405787A JPH01176096A (en) | 1987-12-29 | 1987-12-29 | Composite electroplated steel sheet having high corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01176096A true JPH01176096A (en) | 1989-07-12 |
| JPH0433877B2 JPH0433877B2 (en) | 1992-06-04 |
Family
ID=18273025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33405787A Granted JPH01176096A (en) | 1987-12-29 | 1987-12-29 | Composite electroplated steel sheet having high corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01176096A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009529583A (en) * | 2006-03-10 | 2009-08-20 | マツクス−プランク−ゲゼルシャフト ツール フエルデルング デル ヴイツセンシャフテン エー フアウ | Corrosion Inhibitor Pigment Containing Corrosion Inhibitor Nano Leather Bar |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54159342A (en) * | 1978-06-08 | 1979-12-17 | Nippon Steel Corp | Manufacture of corrosion resistant zinc composite- electroplated steel products |
| JPS60141898A (en) * | 1983-12-29 | 1985-07-26 | Nippon Steel Corp | Composite electroplated steel sheet and its production |
| JPS61127900A (en) * | 1984-11-22 | 1986-06-16 | Kawasaki Steel Corp | Composite plating method |
-
1987
- 1987-12-29 JP JP33405787A patent/JPH01176096A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54159342A (en) * | 1978-06-08 | 1979-12-17 | Nippon Steel Corp | Manufacture of corrosion resistant zinc composite- electroplated steel products |
| JPS60141898A (en) * | 1983-12-29 | 1985-07-26 | Nippon Steel Corp | Composite electroplated steel sheet and its production |
| JPS61127900A (en) * | 1984-11-22 | 1986-06-16 | Kawasaki Steel Corp | Composite plating method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009529583A (en) * | 2006-03-10 | 2009-08-20 | マツクス−プランク−ゲゼルシャフト ツール フエルデルング デル ヴイツセンシャフテン エー フアウ | Corrosion Inhibitor Pigment Containing Corrosion Inhibitor Nano Leather Bar |
| US9340676B2 (en) | 2006-03-10 | 2016-05-17 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigment comprising nanoreservoirs of corrosion inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0433877B2 (en) | 1992-06-04 |
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