JPH01176099A - Composite electroplated steel sheet having high corrosion resistance - Google Patents
Composite electroplated steel sheet having high corrosion resistanceInfo
- Publication number
- JPH01176099A JPH01176099A JP33405887A JP33405887A JPH01176099A JP H01176099 A JPH01176099 A JP H01176099A JP 33405887 A JP33405887 A JP 33405887A JP 33405887 A JP33405887 A JP 33405887A JP H01176099 A JPH01176099 A JP H01176099A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- steel sheet
- plating layer
- alloy
- corrosion
- 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
- 238000005260 corrosion Methods 0.000 title claims abstract description 70
- 230000007797 corrosion Effects 0.000 title claims abstract description 70
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 67
- 239000010959 steel Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims description 46
- 238000007747 plating Methods 0.000 claims abstract description 68
- 239000010419 fine particle Substances 0.000 claims abstract description 62
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 229910000640 Fe alloy Inorganic materials 0.000 claims abstract description 15
- 229910052745 lead Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin 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 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000010408 film Substances 0.000 claims description 30
- 238000011282 treatment Methods 0.000 claims description 23
- 230000002401 inhibitory effect Effects 0.000 claims description 17
- 239000010409 thin film Substances 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 39
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 15
- 239000003973 paint Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000010828 elution Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910007567 Zn-Ni Inorganic materials 0.000 description 4
- 229910007614 Zn—Ni Inorganic materials 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- BYFGZMCJNACEKR-UHFFFAOYSA-N Al2O Inorganic materials [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 3
- 229910021555 Chromium Chloride 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
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 Co Substances 0.000 description 2
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 2
- 229910019142 PO4 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
- 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
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 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
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 description 1
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- 239000004698 Polyethylene 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
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action 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
- 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
- 230000004888 barrier function Effects 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
- 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
- 238000005336 cracking Methods 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
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005755 formation reaction 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
- 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
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 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
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、Ｚｎ−Ｆｅ系合金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と５ｉｎ２．
ＴｉＯ□等の微粒子とを混合して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 Application Field) The present invention provides a Zn-Fe alloy plating layer coated with a thin film of an inorganic or organic material (this treatment will be referred to as microencapsulation). Corrosion inhibiting particulates and 5in2.
This invention relates to a highly corrosion-resistant electrolytic composite plated steel sheet containing a mixture of fine particles such as TiO□.
（従来の技術）
、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などが
散布されており、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。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０本発明は、後者
に関するもので、薄日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。(Conventional technology) 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. ing. 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. 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. The present invention relates to the latter, and to date, thin-dated electroplated steel sheets have been developed using zinc alloy plated steel sheets such as Zn-Fe, Zn-Ni, Zn-Mn, etc. Organic multilayer electroplated steel sheets have been developed in which a chromate + organic resin coating is applied on a Zn or Zn-Ni alloy plating layer.
しかし、上記合金めっきおよび有機複層電気めっき鋼板
は２０〜３０ｇ／＋”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Ｍ２Ｓ年（自動車外面
部に赤錆が５年間発生しないこと）−“謝礼あき１０年
（自動車外面および内面からの孔あきがｌＯ年間生じな
いこと）”特に“謝礼あき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。However, the above-mentioned alloy plated and organic multilayer electroplated steel sheets have a light weight of about 20 to 30 g/+'', and currently the goal of domestic and foreign automakers is ``External M2S (no red rust will occur on the exterior of the automobile for 5 years)''. It is said that the requirement of ``10 years after remuneration (no punctures from the outside or inside of the vehicle for 10 years)'' has not yet been met, especially ``10 years after remuneration''. 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あり、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６
０−９６７８６号公報、特開昭６０−２１１０９４〜２
１１０９６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 plating layer through dispersed and eutectoid fine particles, and are increasingly being used as plated steel sheets with new functions. For example, recently, composite plated steel sheets that exhibit high corrosion resistance have been developed.
Publication No. 0-96786, JP-A-60-211094-2
It has been introduced in many patent publications such as No. 11096.
特開昭６０−９６７８６号公報は、ＺｎやＺｎ−Ｎｉ合
金めっき層中に、防錆顔料（例えばＰｂＣｒ０い５ｒＣ
ｒＯいＺｎＣｒ０．、 ＢａＣｒＯ４，ｚｎｉ（ｐｏＪ
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端や謝礼あきに対
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のみ（水溶液中で、は
とんど溶解しない）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／ｍ”）は謝礼あき１０年レベルにあり
、比較材として使用した。JP-A-60-96786 discloses that anticorrosion pigments (for example, PbCr0, 5rC, etc.) are added to the Zn or Zn-Ni alloy plating layer.
rOZnCr0. , BaCrO4,zni(poJ
This paper describes a composite plated steel sheet with dispersion and eutectoid dispersion (e.g., z) and its manufacturing method. This composite plated steel sheet can be evaluated as having superior corrosion resistance to outer surface edges and cracking compared to the alloy plating and organic multilayer electroplating. However, as disclosed in JP-A No. 60-96786, a plated steel sheet containing only a slightly soluble chromate anti-rust pigment (which hardly dissolves in an aqueous solution) is the target of the present inventors. Corrosion resistance level has not been reached. The results of the accelerated corrosion test conducted by the present inventors are shown in FIG. Here, the hot-dip galvanizing (90 g/m'') was at the level of 10 years of remuneration 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
めっき鋼板のは、溶融亜鉛めっき鋼板（９０ｇ／ｍ”
）■に比べ謝礼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、亜鉛めっき浴中
において表面電位がほぼゼロであるため、めっき浴中で
鋼板を陰極にして電解処理しても浴中Ｚｎ”＋イオンが
優先析出し、防錆顔料のめっ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合金めっき層中に、クロム、アルミナ（
Ａ１２０．）、シリカ（Ｓｕｎ、）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、Ｃ
ｒ ３ ＋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（Ｃ
ｒ、Ｏ，−ｎＨ，Ｏ）が析出し、めっき層はＺｎ−Ｎ１
−Ｃｒ（＋Ｃｒ、Ｏ，・ｎ）Ｉ、 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、Ｚ
ｎ−Ｎ１−Ｃｒ（＋Ｃｒ２Ｏ３・ｎＨ３Ｏ）めっき層に
比べ、耐食性向上幅が小さく、第１図にＺｎ−Ｎｉ−Ｃ
ｒ−Ａｌ２Ｏ３系複合めっき鋼板■の腐食促進試験結果
を示すように、謝礼あき１０年を満足するまでには至っ
ていない。すなりち、Ｚｎ−Ｎｉ−Ｃｒ−Ａｌ２Ｏ，系
複合めっき鋼板もやはり溶融亜鉛めっき鋼板（９０ｇ／
ａ２）の謝礼あき性に及ばない。The composite plated steel sheet in which only BaCrO4 particles are dispersed in the Zn plating is hot-dip galvanized steel sheet (90g/m”
)■ The remuneration 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 anti-rust pigments such as poorly soluble chromates have a surface potential of almost zero in a galvanizing bath. However, Zn''+ ions preferentially precipitate in the bath, making it difficult for the anti-rust pigment to precipitate onto the plating layer, and as a result, a composite plated steel sheet with stable corrosion resistance cannot be obtained. The publication states that chromium, alumina (
A120. ), silica (Sun, ), etc. are dispersed and eutectoided to form a composite plated steel sheet. In this publication, chromium chloride (CrCL) is used as a chromium source in the plating bath, but chromium chloride dissolves in the plating bath, resulting in
Release r 3 + ions. When electrolytically treated in this bath with a steel plate as the cathode, metallic chromium and chromium oxide (C
r, O, -nH, O) is precipitated, and the plating layer is Zn-N1
-Cr (+Cr, O, .n) I, O), and a composite plated steel sheet is produced in which alumina and silica are eutectoid. This composite plated steel sheet has Zn-Ni alloy plating, Z
Compared to the n-N1-Cr (+Cr2O3/nH3O) plating layer, the improvement in corrosion resistance is smaller, and as shown in Figure 1, the Zn-Ni-C
As shown in the accelerated corrosion test results for r-Al2O3 composite plated steel sheet (2), the 10-year remuneration requirement has not yet been met. Sunarichi, Zn-Ni-Cr-Al2O system composite plated steel sheet is also hot-dip galvanized steel sheet (90g/
It is not as generous as a2).
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％Ｂａ（、ｒ０４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％ＡＩ、０３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． （Ｓ
ｉｎ、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と５ｌｏｔｓ ＴｘＯ２，Ｃ
ｒｚＯ３＋ Ａ１１ａｓ、ＺｒＯ，、５ｎ０２ｙｓｂ２
ｏ、の微粒子又はコロイド粒子を分散共析させためつき
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、謝礼あき性にすぐれて
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%Ba (, r04 composite plated steel plate (plated under the conditions of JP-A-60-96786)2:
Zn-1%Ni-1%Cr-1%AI, 03 composite plated steel sheet (plated under the conditions disclosed in JP-A-60-211095) 3: Zn-10%C0-4%BaCr0. (S
in, 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, microparticles and 5 lots of TxO2,C are encapsulated by surface coating with an extremely thin film.
rzO3+ A11as, ZrO,, 5n02ysb2
The plated steel sheet ■, which is coated with a layer made of dispersed eutectoid fine particles or colloidal particles, has excellent properties as a rust-preventing steel sheet for automobiles, and is particularly excellent in rust resistance and corrosion resistance. I found it.
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と、５１０２＋ Ｔｌ０ｚｙ
Ｃｒ２０． Ａｌ、Ｏ，、ＺｒＯ，、ＳｎＯ，、Ｓｂ、
０．の微粒子あるい、はそのコロイド粒子の１種又は２
種以上を混合して含有する、Ｚｒｘ−Ｆｅ合金あるいは
Ｍｎ、 Ｃｒ、Ｓｎｔ Ｓｂ。That is, the gist of the present invention is as follows: (1) 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, and 5102+ Tl0zy
Cr20. Al, O,, ZrO,, SnO,, Sb,
0. or one or two of its colloidal particles.
Zrx-Fe alloy or Mn, Cr, Snt Sb containing a mixture of at least one species.
Ｐｂ、 Ｍｏの１種又は２種以上を含有し・たＺｎ−Ｆ
ｅ系合金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。Zn-F containing one or more of Pb and Mo
A highly corrosion-resistant electro-composite plated steel sheet characterized by having an e-based alloy plating layer.
（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と、Ｓｉｎ、 、 ＴｉＯ２
゜Ｃｒ２Ｏ，、Ａ１２０１． ＺｒＯ２，ＳｎＯ，、Ｓ
ｂ、Ｏｓ の微粒子あるいはそのコロイド粒子の１種又
は２種以上を混合して含有する、Ｚｎ−Ｆｅ合金あるい
はＭｎ、 Ｃｒ、Ｓｎ、 Ｓｂ。(2) Corrosion inhibiting fine particles coated on one or both sides of a steel plate with an ultra-thin film of an inorganic or organic substance, and Sin, TiO2
゜Cr2O,, A1201. ZrO2, SnO,,S
b, Zn-Fe alloy or Mn, Cr, Sn, Sb containing one type or a mixture of two or more of fine particles of Os or colloidal particles thereof.
Ｐｂ、 Ｍｏの１種又は２種以上を含有したＺｎ−Ｆｅ
系合金めっき層を有し、その上にＺｎ、 Ｆｅ、 Ｃｏ
、 Ｎｉ、 Ｍｎ。Zn-Fe containing one or more of Pb and Mo
Zn, Fe, Co
, Ni, Mn.
Ｃｒの１種又は２種以上からなる電気めっき１１〜５ｇ
１ｒｒｒ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。11 to 5 g of electroplating consisting of one or more types of Cr
A highly corrosion resistant electro-composite plated steel sheet characterized by having a corrosion resistance of 1rrr.
（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と、ＳｉＯ２，ＴｉＯ□。(3) Corrosion inhibiting fine particles coated on one or both sides of a steel plate with an ultra-thin film of an inorganic or organic substance, and SiO2, TiO□.
Ｃｒ２Ｏ３ｖ Ａ１２０３ ＋ ＺｒＯ２ｔ ＳｎＯ，
ｌ Ｓｂ２０５ の微粒子あるいはそのコロイド粒子の
１種又は２種以上を混合して含有する、Ｚｎ−Ｆｅ合金
あるいはＭｎ、 Ｃｒ、Ｓｎ、 Ｓｂ。Cr2O3v A1203 + ZrO2t SnO,
l Zn-Fe alloy or Mn, Cr, Sn, Sb containing one type or a mixture of two or more of fine particles of Sb205 or colloidal particles thereof.
Ｐｂ、 Ｎｏの１種又は２種以上を含有したＺｎ−Ｆｅ
系合金めっき層を有し、その上に有機樹脂皮膜、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。Zn-Fe containing one or more of Pb and No.
1. A highly corrosion-resistant electrolytically composite plated steel sheet, which has a plating layer based on the alloy, and has any one of an organic resin film, an organic resin film after chromate treatment, and an organic resin film containing chromium ions thereon.
（４） ！Ｗ板の片面又は画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と、ＳｉＯ□ｌ Ｔｘ０
２゜Ｃｒ、０３． Ａｌ２Ｏ，、ＺｒＯ，、５ｎ０２．
ｓｂ、ｏ、の微粒子あるいはそのコロイド粒子の１種
又は２種以上を混合して含有する、Ｚｎ−Ｆｅ合金ある
いはＭｎ、 Ｃｒ、Ｓｎ、 Ｓｂ。(4)! Corrosion inhibiting fine particles coated with an ultra-thin film of inorganic or organic material on one side or screen of the W plate, and SiO□l Tx0
2°Cr, 03. Al2O,, ZrO,, 5n02.
Zn-Fe alloy or Mn, Cr, Sn, Sb containing one type or a mixture of two or more of fine particles of sb, o, or colloidal particles thereof.
Ｐｂ、 Ｍｏの１種又は２種以上を含有したＺｎ−Ｆｅ
系合金めっき層を有し、その上にＺｎ＋ Ｆｅｇ Ｃｏ
ｇ Ｎｉ、 Ｍｎ。Zn-Fe containing one or more of Pb and Mo
Zn + Feg Co
g Ni, Mn.
Ｃｒの１種又は２種以上からなる電気めっきＭ１〜５ｇ
／ｍ２を有し、その上に有機樹脂皮膜、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−樹脂皮
膜のいず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。Electroplating M1-5g consisting of one or more types of Cr
/m2, and on which any one of an organic resin film, an organic resin film after chromate treatment, and an organic resin film containing chromium ions is laminated. .
（作 用）
本発明の複合めっき鋼板の構造について詳細に説明する
。第２図（ａ）、（ｂ）、（Ｃ）、（ｄ）は本発明複合
めっき鋼板モデルの断面図を示したものである。(Function) The structure of the composite plated steel sheet of the present invention will be explained in detail. 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Ｍｎ
、 Ｃｒ。2 is Zn-Fe alloy plating or Mn 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
着されている。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腐食阻止微粒子である
。3 is microencapsulated corrosion inhibiting fine particles.
４はＺｎ−Ｆｅ合金めっき層■などに分散しあるいはマ
イクロカプセル微粒子■に付着した５ｉｎ２゜Ｔｉｅ、
、 Ｃｒ、Ｏ３、Ａｌ、Ｏ，、ＺｒＯ，、ＳｎＯ，、Ｓ
ｂ、Ｏ，の１種又は２種以上の微粒子またはそのコロイ
ド粒子であるゆ
マイクロカプセル化される腐食阻止微粒子は、難溶性ク
ロム酸塩微粒子（ＰｂＣｒＯ４，ＢａＣｒＯ４，５ｒＣ
ｒＯ，、ＺｎＣｒ０９等）、易溶性クロム酸塩（Ｃｒｙ
、、Ｎａ、Ｃｒｙ、、 Ｋ、ＣｒＯ４，Ｋ、０・４Ｚｎ
０・４ＣｒＯ，等）、アルミ化合物（Ｚｎ−Ａ１合金粉
末、Ａｌ、Ｏ，・２ＳｉＯ，・２Ｈ２０等）、リン酸塩
（Ｚｎ、 （ＰＯ，）２−２Ｈ，Ｏ等）、モリブデン化
合物（ｚｎＯ・ｚｎＭ００イＣａ０Ｍ００４・Ｚｎ０Ｍ
００４．ＰｂＣｒ０１・ＰｂＭ００４・ｐｂｓｏ、等）
、チタン化合物（Ｔｉｅ２・ＮｉＯ・５ｂ２ｏ、等）を
はじめとした無機物粒子、又は弗素樹脂、ポリエチレン
樹脂等の有機物粒子のいずれでもよい。4 is a 5in2° Tie dispersed in a Zn-Fe alloy plating layer (■) or attached to a microcapsule particle (■);
, Cr, O3, Al, O,, ZrO,, SnO,, S
The corrosion inhibiting fine particles to be microencapsulated are fine particles of one or more types of B, O, or colloidal particles thereof.
rO, ZnCr09, etc.), easily soluble chromate (Cry
,,Na,Cry,,K,CrO4,K,0・4Zn
0.4CrO, etc.), aluminum compounds (Zn-A1 alloy powder, Al, O, .2SiO, .2H20, etc.), phosphates (Zn, (PO,)2-2H, O, etc.), molybdenum compounds (ZnO・znM00iCa0M004・Zn0M
004. PbCr01・PbM004・pbso, etc.)
, inorganic particles such as titanium compounds (Tie2, NiO, 5b2o, etc.), or organic particles such as fluororesin and polyethylene 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
、ＳｉＯ２、Ｔｉｅ２． ＡＬ、 Ｏ，、ＺｒＯ□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。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。The ultrathin film for micro-encapsulating fine particles as described above is SiO2, Tie2. It consists of one or more inorganic substances such as AL, O, ZrO□, and organic substances such as ethyl cellulose, amino resin, vinylidene chloride resin, polyethylene, and polystyrene. 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. By microencapsulating particles, the following effects occur.
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。しかし、Ｓｉｎ、、Ｔｉｅ、
、Ａｌ、Ｏ，、ＺｒＯ，等の微粒子又はコロイド粒子は
、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、マ
イクロカプセル化することにより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。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. However, Sin,,Tie,
, Al, O, ZrO, etc., have potential themselves, and this property does not change even if the surface of the particles is coated. It is possible to impart a potential to 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Ｃ，ｊ＋イオンが一定濃
度以上になると、微粒子の析出量が低下したり、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 C,j+ ions exceeds a certain level, the amount of fine particles precipitated 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、Ｃｒ
’＋イオンを放出する。このＣｒ’＋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。When poorly soluble chromate fine particles are dispersed and eutectoid, they decompose as the corrosion of the plating layer progresses in a corrosive environment, and Cr
' Releases + ions. These Cr'+ 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つき溜全
体に微粒子が均一分散していることがら、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, the fine particles are uniformly dispersed throughout the plating reservoir, so 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はなく、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
ｒｉ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１７３〜１／１０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。Next, when microencapsulated fine particles are used, corrosion resistance is further improved. Since the film of microencapsulated Sin, etc. is not completely sealed but porous, Cr"+ ions are eluted little by little, forming a rust-preventing film made of chromium compounds and improving corrosion resistance. is the same as that of non-encapsulated microparticles.However, in the case of microencapsulated sparingly soluble chromate particles, the C
By suppressing the elution rate of ri ions (according to experiments conducted by the inventors, the rate is 173 to 1/10), a significant feature is that the lifespan of forming a rust preventive film is extended accordingly.
自動単向防錆鋼板の射孔あき寿命は前述の如＜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。As mentioned above, the perforation life of the automatic unidirectional rust-preventing steel plate is aimed at a long term of <10 years, and the accelerated corrosion test conducted in the experiment is also a long-term one of 1% and 3 months.
従って、めっき層中の分散粒子が一時的にＣｒＳ ＋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 the dispersed particles in the plating layer temporarily releasing CrS + ions to form a thick anti-rust film made of chromium compounds, the dispersed particles in the plating layer gradually release Cr'+ ions to repeatedly form a thin anti-rust film. This provides 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（ ｒ ｉ ４）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ＰＯ４３−イオン、モリ
ブデン化合物から溶出するＭ００４２−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０．５〜２Ｃｈ
ｔ％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 (r i 4) ions eluted from poorly soluble chromate fine particles, but the anticorrosion effect also applies to PO43- ions eluted from phosphate compounds and M0042- ions eluted from molybdenum compounds. are the same. According to experiments conducted by the inventors, the content of microencapsulated fine particles is preferably 0.1 to 30 wt% of the coating weight (preferably 0.5 to 2 Ch).
t% is good). 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.
さらに、マイクロカプセル化された微粒子と同時にめっ
き層に分散共析されるＳｉｎ、、 ＴｉＯ□。Furthermore, Sin, TiO□ are dispersed and co-deposited in the plating layer at the same time as the microencapsulated fine particles.
Ｃｒ、０． 、 Ａ１．Ｏ，、ＺｒＯ，、ＳｎＯ２，Ｓ
ｂ、Ｏｓ の微粒子は、難溶性クロム酸塩微粒子と違っ
て、腐食阻止作用は小さい。しかし、マイクロカプセル
化された粒子が析出しない部分に析出することで、部分
めっき層の腐食進行を抑制する。つまり、めっき層に対
して、腐食因子の攻撃に対するバリアー効果を有するも
のである。Ｓｉｎ、等微粒子の含有量はめっき付着量の
０．１〜３０ｗｔ％がよい（望ましくは、０．５〜２０
ｗｔ％がよい）。０．１％より低ければ耐食性の向上効
果がなく、３０％を越えるとめっき加工密着性が劣化す
る傾向にある。但し、マイクロカプセル化微粒子とＳｉ
Ｏ□等微粒子の加算含有量は、めっき付着量の３０％を
越えない方がよい。次に、マイクロカプセル化された微
粒子やＳｉＯ□等の微粒子のめっき層への分散共析量を
促進するための添加剤としてＴｉｅ、コロイド、Ａｌ、
Ｏ，コロイド、ＳｉＯ□コロイド、ＺｒＯ２コロイド、
ＳｎＯ□コロイド、ｓｂ、 ｏ５コロイド等の添加が有
効である。Cr, 0. , A1. O,, ZrO,, SnO2,S
b, Os 2 fine particles have a small corrosion inhibiting effect, unlike sparingly soluble chromate fine particles. However, the microencapsulated particles precipitate in areas where they do not precipitate, thereby suppressing the progress of corrosion of the partial plating layer. In other words, it has a barrier effect on the plating layer against attack by corrosive factors. The content of fine particles such as Sin is preferably 0.1 to 30 wt% of the coating weight (preferably 0.5 to 20 wt%).
wt% is better). If it is less than 0.1%, there is no effect of improving corrosion resistance, and if it exceeds 30%, plating adhesion tends to deteriorate. However, microencapsulated fine particles and Si
The additional content of fine particles such as O□ should not exceed 30% of the amount of plating deposited. Next, Tie, colloid, Al,
O, colloid, SiO□ colloid, ZrO2 colloid,
Addition of SnO□ colloid, sb, o5 colloid, etc. is effective.
マイクロカプセル化により、微粒子の表面電位コントロ
ールが可能なことは前述したが、ＳｉＯ□薄膜の場合は
、微粒子は″負″の電位を有することになる。鋼板を陰
極として電解処理する電気めっき法においては、ＳｉＯ
□薄膜カプセル化微粒子はめっき層へ析出し難い。その
ため上記添加剤により、めっき層への分散共析量を増大
させる必要がある。As mentioned above, it is possible to control the surface potential of fine particles by microencapsulation, but in the case of a SiO□ thin film, the fine particles have a "negative" potential. In the electroplating method, which uses a steel plate as a cathode for electrolytic treatment, SiO
□Thin-film encapsulated fine particles are difficult to deposit on the plating layer. Therefore, it is necessary to increase the amount of eutectoid dispersion into the plating layer using the above additive.
例えば、Ａｌ、Ｏ，コロイドは、正の電荷を有し、何ら
かの作用（明確ではない）により、Ｓｕｎ、薄膜でカプ
セル化された微粒子の表面に吸着を起こす。For example, Al, O, and colloids have a positive charge, and due to some action (not clear) they cause adsorption on the surface of fine particles encapsulated in a thin film.
これにより、微粒子は正の電荷（電位）を有することに
なり、電解時に容易に陰極へ引きつけられる。すなわち
、めっき層への充分な析出が可能となる。他のコロイド
粒子についても同様な反応が起っていると考えられる。As a result, the fine particles have a positive charge (potential) and are easily attracted to the cathode during electrolysis. That is, sufficient precipitation onto the plating layer becomes possible. It is thought that similar reactions occur with other colloidal particles.
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、射孔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射孔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Ｚｎ、 Ｆｅ、 Ｃｏ。The composite plating layer obtained in this way exhibits sufficient performance in terms of rust resistance and perforation resistance as described above, but 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 carried out as a chemical conversion treatment, does not react on chromium, so it may cause the coating crystals to become coarser or cause scratches (crystals are not formed), which may lead to variations in paint adhesion after painting and shot holes after painting. It becomes a factor that occurs. Therefore, when painting automobile exterior panels, etc., Zn, Fe, and Co are coated on the composite plating layer as shown in FIG. 2(b).
Ｎｉ、 Ｍｎ、 Ｃｒの１種又は２種以上からなる電気
薄めっき層■を１〜５ｇ／ｍ施こす、この電気めっき層
■がＩｇ／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／ｒｒｒ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、 Ｍｎ、Ｃｒの１種又は２
種以上から成るめっき層を多重処理してもよい。但しそ
の場合の全付着量は、１〜５ｇ／ｒｒｒでコントロール
するのは前記理由と同じである。Apply a thin electroplating layer (■) of 1 to 5 g/m consisting of one or more of Ni, Mn, and Cr. If this electroplating layer (■) is less than Ig/m, completely cover the composite plating layer. If it exceeds 5 g/rrr, the plating adhesion tends to deteriorate slightly, so it is better to control it within the above range.
is one or two of Zn, Fe, Co, Mn, Cr
A plating layer consisting of more than one type may be subjected to multiple treatments. However, in that case, the total amount of adhesion is controlled at 1 to 5 g/rrr 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射孔あ
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Ｓｉｎ、、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 perforation properties after painting. This effect is caused by the fact that the material of the capsule enclosing the corrosion-inhibiting particles is Sin, 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.
あるいは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ート皮膜中のクロム（特にＣｒ
＠＋イオン）の溶出が懸念される。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←
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。Alternatively, in order to further improve corrosion resistance, chromate treatment may be performed on the composite plating layer. but,
Chromate treatment alone can remove chromium (especially Cr) in the chromate film during degreasing and chemical conversion treatment in the automobile production process.
There is a concern about the elution of @+ ions). 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 (elution size ←
(Applicable chromate>Reactive chromate>Electrolytic chromate→Low elution) Corrosion resistance is in the reverse order of elution. 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
含有したものが使用される。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Ｚｎ−Ｆｅ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。Plating is performed by electrolytically treating the steel plate in a sulfuric acid 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
例えば
Ｚｎ−Ｆｅ−ＢａＣｒ０． （Ｓｉｎ、薄膜コート粒子
）−Ａ１．０．複合めっきの場合には、
膜厚はｌ０Ａ−１μのものを虐亘用いたり次に、複合め
っきの上に行なう薄電気めっきについては、硫酸酸性浴
系で、Ｚｎ、 Ｆｅ、 Ｃｏ、 Ｎｉ、 Ｍｎ、Ｃｒの
硫酸塩を適当量添加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。For example, Zn-Fe-BaCr0. (Sin, thin film coated particles) -A1.0. In the case of composite plating, a film with a thickness of 10A-1μ is used.Next, for thin electroplating on the composite plating, Zn, Fe, Co, Ni, Mn are used in a sulfuric acid acid bath system. Using a plating bath to which an appropriate amount of Cr sulfate was added, the total deposition amount was in the range of 1 to 5 g/m.
また、樹脂塗装およびクロムを含有した樹脂塗装は、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。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、反応および電解のいずれの
タイプでも行なった。Further, the resin coating and the resin coating containing chromium were performed by a roll coating method using a water-soluble acrylic emulsion system as the resin. In addition, for chromate-treated resin coating, resin coating is performed using the roll coating method.
For chromate, coating, 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 manner.
（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：塩水噴霧（３５℃Ｘ ６Ｈｒ）、乾燥（
７０℃、６０％Ｘ ４Ｈｒ）、湿潤（４９℃、〉９５％
Ｘ ４Ｈｒ）、冷凍（−２０℃ｘ４Ｈｒ）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２ｍ■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 6 hours), drying (
70℃, 60%×4Hr), wet (49℃, 〉95%
x 4Hr) and freezing (-20℃ x 4Hr),
This is one cycle of composite corrosion test (2) Paint adhesion ■ Treatment: Full-dip type chemical conversion treatment → 3-coat painting → Warm water immersion (40°C x 10 days) ■ Evaluation: After the test, 2 m squares x 100 squares It was placed,
Measurement of paint film peeling rate by taping (3) Evaluation of red rust occurrence rate was performed as follows.
Ｏ・・・赤錆発生率 ０％
Ｏ・・・ 〃 ５％以下
Δ・・・ 〃 ５〜２０％
×・・・ ７Ｆ ２０〜５０％ＸＸ・・・
〃５０％以上
（４）腐食深さの評価は次のようである。O... Red rust occurrence rate 0% O... 〃 5% or less Δ... 〃 5-20% ×... 7F 20-50% XX...
〃50% or more (4) Evaluation of corrosion depth is as follows.
Ｏ・・・腐食深さ Ｏｍ■
○・・・ ９０．１ｍｍ以下
Δ・・・ 〃０．１〜０．３ｍｍ
Ｘ・・・ 〃 ０．３〜０
．５＋鳳ＸＸ・・・ ” ０．５ｍ職以上
（５）塗料密着性の評価は次のようである。O... Corrosion depth Om ■ ○... 90.1mm or less Δ... 〃0.1~0.3mm X...〃 0.3~0
．． 5 + Otori XX..." 0.5 m or more (5) Evaluation of paint adhesion is as follows.
Ｏ・・・塗膜剥離率 ０％
０・・・ 〃 ５％以下
Δ・・・ 〃 ５〜２０％
×・・・ 〃２０〜５０％
ＸＸ・・・ 〃５０％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。O... Paint film peeling rate 0% 0... 〃 5% or less Δ... 〃 5-20% ×... 〃20-50% XX... 〃50% 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）
本発明はＳｉｎ、等の極薄膜で表面被覆された腐食阻止
微粒子とＳｉｎ、、 ＴｉＯ２等の微粒子あるいはコロ
イド粒子を合わせて分散共析させたＺｎ−Ｆｅ系電気め
っき複合鋼板は、従来のＺｎ−Ｆｅ合金めっきに比し耐
赤錆性や射孔あき性にすぐれ、さらに薄電気めっきや樹
脂塗装を施こすことで、塗装機耐食性や塗料密着性をも
格段に向上する。(Effects of the Invention) The present invention provides a Zn-Fe electroplated composite steel sheet in which corrosion-inhibiting fine particles whose surface is coated with an ultra-thin film such as Sin and fine particles or colloidal particles such as Sin and TiO2 are dispersed and eutectoid. It has superior red rust resistance and perforation resistance compared to conventional Zn-Fe alloy plating, and by applying thin electroplating and resin coating, paint machine corrosion resistance and paint adhesion are also significantly improved.
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。
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
。
第１図
評価サンプルFigure 1 shows the corrosion depth results for the composite plated steel sheets of the present invention and comparative materials. FIG. 2 shows a cross-sectional view of a composite plated steel plate model of the present invention. Figure 1 Evaluation sample
Claims (4)
で被覆した腐食阻止微粒子と、ＳｉＯ＿２、ＴｉＯ＿２
、Ｃｒ＿２Ｏ＿３、Ａｌ＿２Ｏ＿３、ＺｒＯ＿２、Ｓｎ
Ｏ＿２、Ｓｂ＿２Ｏ＿５の微粒子あるいはそのコロイド
粒子の１種又は２種以上を混合して含有する、Ｚｎ−Ｆ
ｅ合金あるいはＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの
１種又は２種以上を含有したＺｎ−Ｆｅ系合金めっき層
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) Corrosion inhibiting fine particles coated on one or both sides of a steel plate with an ultra-thin film of inorganic or organic matter, SiO_2, TiO_2
, Cr_2O_3, Al_2O_3, ZrO_2, Sn
Zn-F containing one type or a mixture of two or more of fine particles of O_2, Sb_2O_5 or colloidal particles thereof
A highly corrosion-resistant electro-composite plated steel sheet comprising a plating layer of e-alloy or a Zn-Fe alloy containing one or more of Mn, Cr, Sn, Sb, Pb, and Mo.
で被覆した腐食阻止微粒子と、ＳｉＯ＿２、ＴｉＯ＿２
、Ｃｒ＿２Ｏ＿３、Ａｌ＿２Ｏ＿３、ＺｒＯ＿２、Ｓｎ
Ｏ＿３、Ｓｂ＿２Ｏ＿５の微粒子あるいはそのコロイド
粒子の１種又は２種以上を混合して含有する、Ｚｎ−Ｆ
ｅ合金あるいはＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの
１種又は２種以上を含有したＺｎ−Ｆｅ系合金めっき層
を有し、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１〜５ｇ／ｍ
＾２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) Corrosion inhibiting fine particles coated on one or both sides of a steel plate with an ultra-thin film of inorganic or organic matter, SiO_2, TiO_2
, Cr_2O_3, Al_2O_3, ZrO_2, Sn
Zn-F containing one type or a mixture of two or more of fine particles of O_3, Sb_2O_5 or colloidal particles thereof
It has a plating layer of e alloy or a Zn-Fe alloy containing one or more of Mn, Cr, Sn, Sb, Pb, and Mo, and on top of that, Zn, Fe, Co, Ni, Mn, and Cr.
1 to 5 g/m of electroplated layer consisting of one or two or more of
A highly corrosion-resistant electro-composite plated steel sheet characterized by having ^2.
で被覆した腐食阻止微粒子と、ＳｉＯ＿２、ＴｉＯ＿２
、Ｃｒ＿２Ｏ＿３、Ａｌ＿２Ｏ＿３、ＺｒＯ＿２、Ｓｎ
Ｏ＿２、Ｓｂ＿２Ｏ＿５の微粒子あるいはそのコロイド
粒子の１種又は２種以上を混合して含有する、Ｚｎ−Ｆ
ｅ合金あるいはＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの
１種又は２種以上を含有したＺｎ−Ｆｅ系合金めっき層
を有し、その上に有機樹脂皮膜、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) Corrosion inhibiting fine particles coated on one or both sides of a steel plate with an ultra-thin film of inorganic or organic matter, SiO_2, TiO_2
, Cr_2O_3, Al_2O_3, ZrO_2, Sn
Zn-F containing one type or a mixture of two or more of fine particles of O_2, Sb_2O_5 or colloidal particles thereof
It has an e-alloy or a Zn-Fe alloy plating layer containing one or more of Mn, Cr, Sn, Sb, Pb, and Mo, and has an organic resin film on it, and an organic resin film and chromium after chromate treatment. A highly corrosion-resistant electrolytic composite plated steel sheet comprising any one of an organic resin film containing ions.
で被覆した腐食阻止微粒子と、ＳｉＯ＿２、ＴｉＯ＿２
、Ｃｒ＿２Ｏ＿３、Ａｌ＿２Ｏ＿３、ＺｒＯ＿３、Ｓｎ
Ｏ＿２、Ｓｂ＿２Ｏ＿５の微粒子あるいはそのコロイド
粒子の１種又は２種以上を混合して含有する、Ｚｎ−Ｆ
ｅ合金あるいはＭｎ、Ｃｒ、Ｓｎ、Ｓｂ、Ｐｂ、Ｍｏの
１種又は２種以上を含有したＺｎ−Ｆｅ系合金めっき層
を有し、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１〜５ｇ／ｍ
＾２を有し、その上に有機樹脂皮膜、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) Corrosion inhibiting fine particles coated on one or both sides of a steel plate with an ultra-thin film of inorganic or organic matter, SiO_2, TiO_2
, Cr_2O_3, Al_2O_3, ZrO_3, Sn
Zn-F containing one type or a mixture of two or more of fine particles of O_2, Sb_2O_5 or colloidal particles thereof
It has a plating layer of e alloy or a Zn-Fe alloy containing one or more of Mn, Cr, Sn, Sb, Pb, and Mo, and on top of that, Zn, Fe, Co, Ni, Mn, and Cr.
1 to 5 g/m of electroplated layer consisting of one or two or more of
A highly corrosion-resistant electrocomposite plated steel sheet, characterized in that it has an organic resin film, an organic resin film after chromate treatment, or an organic resin film containing chromium ions is laminated thereon.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33405887A JPH01176099A (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 |
|---|---|---|---|
| JP33405887A JPH01176099A (en) | 1987-12-29 | 1987-12-29 | Composite electroplated steel sheet having high corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01176099A true JPH01176099A (en) | 1989-07-12 |
| JPH0433878B2 JPH0433878B2 (en) | 1992-06-04 |
Family
ID=18273036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33405887A Granted JPH01176099A (en) | 1987-12-29 | 1987-12-29 | Composite electroplated steel sheet having high corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01176099A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03253598A (en) * | 1990-03-02 | 1991-11-12 | Mitsubishi Electric Corp | Dispersion plating method |
| JP2004263252A (en) * | 2003-03-03 | 2004-09-24 | Jfe Steel Kk | Chromium-free chemically treated steel sheet excellent in resistance to white rust |
| JP2009517545A (en) * | 2005-11-30 | 2009-04-30 | ナノゲート エージー | Silicate coated particles in metal layers |
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 JP33405887A patent/JPH01176099A/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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03253598A (en) * | 1990-03-02 | 1991-11-12 | Mitsubishi Electric Corp | Dispersion plating method |
| JP2714470B2 (en) * | 1990-03-02 | 1998-02-16 | 三菱電機株式会社 | Graphite particle dispersion silver plating method |
| JP2004263252A (en) * | 2003-03-03 | 2004-09-24 | Jfe Steel Kk | Chromium-free chemically treated steel sheet excellent in resistance to white rust |
| JP2009517545A (en) * | 2005-11-30 | 2009-04-30 | ナノゲート エージー | Silicate coated particles in metal layers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0433878B2 (en) | 1992-06-04 |
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