JPH0514789B2 - - Google Patents
Info
- Publication number
- JPH0514789B2 JPH0514789B2 JP62332758A JP33275887A JPH0514789B2 JP H0514789 B2 JPH0514789 B2 JP H0514789B2 JP 62332758 A JP62332758 A JP 62332758A JP 33275887 A JP33275887 A JP 33275887A JP H0514789 B2 JPH0514789 B2 JP H0514789B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- colloidal silica
- organic resin
- resin
- corrosion resistance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011347 resin Substances 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 68
- 238000005260 corrosion Methods 0.000 claims description 27
- 230000007797 corrosion Effects 0.000 claims description 27
- 229910000831 Steel Inorganic materials 0.000 claims description 25
- 239000010959 steel Substances 0.000 claims description 25
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 55
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- 239000008119 colloidal silica Substances 0.000 description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 33
- 239000003973 paint Substances 0.000 description 33
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 31
- 239000011651 chromium Substances 0.000 description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 18
- 239000011701 zinc Substances 0.000 description 18
- 229910052725 zinc Inorganic materials 0.000 description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005246 galvanizing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 230000003666 anti-fingerprint Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- ZNNLBTZKUZBEKO-UHFFFAOYSA-N glyburide Chemical compound COC1=CC=C(Cl)C=C1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)NC2CCCCC2)C=C1 ZNNLBTZKUZBEKO-UHFFFAOYSA-N 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
〔産業上の利用分野〕
本発明は亜鉛めつき、または亜鉛系合金めつき
鋼板上にクロメート皮膜を生成させた、表面処理
鋼板に関するものである。
〔従来の技術とその問題点〕
従来亜鉛めつき鋼板のクロメート処理としてク
ロムを主成分として、Si、Ｐ、有機樹脂を含む皮
膜を生成させることは既知である。
例えば、Siとしてシリカを添加したものとして
特公昭61−58552号公報、特公昭61−1508号公報、
特開昭60−13079号公報、特公昭61−54880号公報
記載のものなどがある。またＰとしてりん酸を添
加したものとして、特公昭53−41621号公報、ま
たSiとＰの双方を添加したものとして特公昭60−
18751号公報記載のものがある。これらは従来の
Crのみのクロメート皮膜の耐食性を更に向上さ
せる他、塗料との密着性を付与することを目的と
したものである。
一方、近年家電製品、事務機器などに用いられ
る鋼板は、亜鉛または亜鉛系合金めつき鋼板を塗
装せずに、または塗装して使用される。すなわち
鋼板に必要な特性は、無塗装での耐食性や外観
（色調、色むら）、製品製作中および使用中に於い
て指紋の着きにくいこと、更に塗装した時の塗料
に密着性等々である。
古くからクロム酸処理によるクロメート皮膜
は、単に耐食性を付与するものであつたが、上記
の種々の特性が要求されるに及んで、Si、Ｐ、金
属イオンが処理液に添加されるようになり、更に
耐指紋性の向上のためには、特開昭61−207579号
公報、特開昭59−140050号公報などに示されるよ
うに、有機樹脂が添加されるようになつた。
しかしながらいずれも要求される性能の全てを
満たすことは難かしく、特に、折り曲げ、絞りな
どの成形加工を行うと、皮膜の破壊が起りめつき
層が露出して、その部位より亜鉛の白錆発生が起
り易くなる欠点を有していた。
（発明が解決しようとする問題点）
本発明は上記の点に鑑み、亜鉛めつきおよび亜
鉛系合金めつき鋼板上のクロメート皮膜の耐食
性、加工部耐食性、塗料密着性、耐指紋性、色む
らの全てを向上させたクロメート皮膜構造を有す
る化成処理鋼板を提供することを目的とする。
（問題点を解決するための手段）
上記目的は下記に示す構成の皮膜を、亜鉛また
は亜鉛系合金めつき鋼板上に形成させることによ
つて有利に達成できる。すなわち、本発明は亜鉛
又は亜鉛系合金めつき鋼板の表面に第一層とし
て、Cr≧５mg／m2、Si≧３mg／m2、Si／Cr＝0.1
〜５からなる第一層皮膜を有し、その上にＰ、
Si、有機樹脂（水溶性または水分散性）のうち、
いずれか２種以上を含み、Ｐ＋Si＋有機樹脂≧１
mg／m2、かつSiを含むときはSi／（Ｐ＋有機樹
脂）＝0.1〜10、Ｐを含むときはＰ／（Si＋有機樹
脂）＝0.1〜10の範囲にある第二層皮膜を有するこ
とを特徴とする加工部耐食性の優れたクロメート
処理鋼板を要旨とするものである。また第二層中
にCrをCr／（Ｐ＋Si＋有機樹脂）≦0.2の範囲で含
有するものも有効である。さらに第二層中にCr
を含む場合、含まない場合のいずれについても、
第一層中に水溶性または水分散性有機樹脂を含む
ものも有効である。
以下、本発明について詳細に説明する。
本発明を構成するに当り、発明者らは上記の諸
性能が皮膜構成成分によつて如何なる影響を受け
るかに関する詳細な検討を行つた。その結果Cr
は耐食性に有効だが色むらの原因になり易く、外
観を損い、また塗料密着性、耐指紋性に不利であ
り、Siは特に塗料一次密着性に有効だが、塗料二
次密着性および耐指紋性に不利であり、またＰは
耐食性と耐指紋性に有利だが塗料一次密着性に不
利であることが判明した。塗料一次密着性とは、
塗料を塗布した直後の鋼板表面と、塗料との密着
性を意味し、塗膜にナイフで１mmのゴバン目100
ケ（10×10）の切込みを入れ、接着テープで剥離
したときの剥離したゴバン目の数で評価したもの
である。（ゴバン目テープ法）塗料二次密着性と
は、塗装した鋼板をある環境下で経時させた後の
塗料密着性を示し、本発明では、100％の湿気槽
内に１週間保持した後、ゴバン目テープ法にて評
価したものである。
加工部耐食性は、180゜折り曲げ加工した試験片
を用いて塩水噴霧にて評価したところCrまたは
Siを少くとも１種以上を含むものが良好で、双方
とも含まないものは折り曲げ部からの白錆が非常
に発生し易いことがわかつた。つまり、Crおよ
びSiは加工部の耐食性確保に必要である。
有機樹脂は耐食性、塗料密着性、耐指紋性のい
ずれにも良い効果を与えるが、他の構成成分に比
べて最も高価であり、多量に含有することは有利
ではない。
ここで諸性能の内容をよく考えてみると、耐食
性、色むらなどはクロメート皮膜全体の性能であ
るのに対し塗料密着性や耐指紋性は皮膜の最表層
部分が示す性能であると考えられる。つまり、最
表層は塗料密着性と耐指紋性に有利な構成とし、
内層は耐食性にすぐれた構成にすれば塗料密着
性、耐指紋性、耐食性の全てを充たすことが可能
となるはずである。また色むらの原因となり易い
Cr成分を内層のみに止めることにより、つまり
最外層から除くことによりまたはその含有量を少
量に限定することにより外観上の問題を解決でき
ることになる。
本発明はこのような考え方に基き、第一層（下
層）にCrとSiとを同時に存在させることを必須
としたものである。両者とも耐食性に有効であ
り、加工部に対してはSiがより有効である。Cr
が５mg／m2未満、Siが３mg／m2未満となると、い
ずれも耐食性が不足する。Si／Crは加工部耐食
性に関係があり0.1未満では加工部耐食性が不足
する。またSi／Crが５を超えると塩水噴霧試験
での耐食性が不良となる。
また第一層皮膜中に水溶性または水分散性有機
樹脂を含有せしめたことは加工部耐食性、平板で
の耐食性をともに向上させる効果がある。
第二層（外層）は塗料一次密着性、塗料二次密
着性、耐指紋性を向上させ、更に第一層の色む
ら、色調を均一化、無色化することを目的とする
層である。樹脂、SiおよびＰが持つこれらの性能
に対する効果は以下の通りである。Siは塗料一次
密着性を向上させるが、塗料二次密着性および耐
指紋性を低下させる。Ｐは塗料一次密着性を低下
させるが、塗料二次密着性の保持に役立ち、耐指
紋性の向上および第一層の色むら、色調の均一
化、無色化に効果を表わす。有機樹脂は塗料一
次、二次密着性の保持に役立ち、耐指紋性につい
ては添加量が一定以上になると向上効果を表わ
す。
従つて有機樹脂、Si、Ｐのうち少なくとも２種
を混合して以下のような範囲の組成をもつ第二層
皮膜を形成すれば、塗料一次、二次密着性、耐指
紋性、外観均一性のすべてを向上させることがで
きる。
第一層の色調・色むらの均一化のためには（有
機樹脂＋Ｐ＋Si）が１mg／m2以上であることが必
要で、それ未満では効果がない。
Siを含むときは、Siの塗料二次密着性の低下効
果を緩和するためにＰ、有機樹脂の少なくとも一
方をSi／（Ｐ＋有機樹脂）≦10の範囲で第二層皮
膜中に含むことが必要で、一方Siの塗料一次密着
性の向上効果を損わないためには、Ｐ、有機樹脂
の量の上限としてSi／（Ｐ＋有機樹脂）≧0.1であ
ることが必要である。
Ｐを含むときは、Ｐの塗料一次密着性の低下効
果を緩和するためにSi、有機樹脂の少なくとも一
方をＰ／（Si＋有機樹脂）≦10の範囲で第二層皮
膜中に含むことが必要で、一方Ｐの耐指紋性向上
効果、塗料二次密着性の保持効果を損わないため
には、Si、有機樹脂の量の上限としてＰ／（Si＋
有機樹脂）≧0.1であることが必要である。
第二層皮膜の均一塗布性のためにはCrの添加
が有効であるが、塗料密着性、耐指紋性を保つた
めにはその添加量は第二層皮膜中にＰ＋Si＋有機
樹脂に対して1/10以下、すなわちCr／（Ｐ＋Si
＋有機樹脂）≦0.2でなければならない。
Crは前記特許公報にも記述されるように、無
水クロム酸、クロム酸塩、重クロム酸塩を水に溶
解することで容易に第一層形成処理液に含有させ
ることができ、従つて第一層皮膜中に含有させる
ことが可能である。この際、Crを３価に還元す
るために還元剤を添加し、第一層皮膜中の６価
Crに対する３価Crの割合を増大することも何ら
支障はない。
Siはシリカ粉、コロイダルシリカ、シランカツ
プリング剤、各種ケイ酸塩を水に溶解または分散
させることにより、またＰはりん酸、ポリリン
酸、りん酸塩を水に添加することにより容易に第
二層形成処理液の作成が可能である。
有機樹脂は、水溶性または水分散性の全てのも
のが適用可能である。
鋼板上への皮膜形成は浸漬−ロール絞り−加熱
乾燥、ロールコーテイング、スプレーコーテイン
グなど通常の塗布クロメートのあらゆる皮膜形成
方法が適用できる。但し第一層皮膜形成後、第二
層皮膜形成までの間に第一層皮膜を乾燥すること
が必要である。それにより、第二層形成処理液中
で第一層の溶出を防止することができる。
本発明の化成処理は最表層が亜鉛または亜鉛系
合金めつきである全ての鋼板に適用できる。亜鉛
めつきとは電気亜鉛めつき、溶融亜鉛めつき、真
空蒸着による亜鉛めつきなど全てを含む。亜鉛系
合金めつきとは、亜鉛−ニツケル、亜鉛−鉄、亜
鉛−アルミなど亜鉛と他の金属１種以上を含むあ
らゆる合金めつき、および、ケイ素、チタン、ア
ルミ、クロムなどの金属酸化物をめつき層中に分
散させたもの全てを含むものである。複数層のめ
つき層を有する場合も最上層が上記亜鉛を含有す
るめつき層であれば適用が可能である。また、片
面めつき、樹脂を間に有する複合鋼板などへも同
様に適用が可能である。
実施例 １
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
(ア) 無水クロム酸2.7ｇ／、コロイダルシリカ
10ｇ／
(イ) 無水クロム酸 ４ｇ／、コロイダルシリカ
10ｇ／
(ウ) 無水クロム酸8.5ｇ／、コロイダルシリカ
10ｇ／
(エ) 無水クロム酸 ４ｇ／、コロイダルシリカ
10ｇ／、アクリルアミド樹脂0.8ｇ／
(オ) 無水クロム酸8.5ｇ／、コロイダルシリカ
1.8ｇ／
(カ) 無水クロム酸8.5ｇ／、コロイダルシリカ
５ｇ／
(キ) 無水クロム酸8.5ｇ／、コロイダルシリカ
1.8ｇ／、アクリルアミド樹脂0.8ｇ／
(ク) 無水クロム酸8.5ｇ／、コロイダルシリカ
10ｇ／、アクリルアミド樹脂0.8ｇ／
を含む水溶液に浸漬、ロール絞り後、乾燥（120
℃、３分）して後りん酸３ｇ／、コロイダルシ
リカ５ｇ／、アクリルアミド樹脂0.8ｇ／、
を含む水溶液に浸漬、引上げ後乾燥（120℃、３
分）した二層クロメート処理鋼板について、特性
を評価した結果を第１表に示す。
第１表より、耐食性、加工部耐食性を確保する
ためには、第１層中のCrは５mg／m2以上、Siは
３mg／m2以上必要であることがわかる。
実施例 ２
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
(ケ) 無水クロム酸40ｇ／、コロイダルシリカ
５ｇ／
(コ) 無水クロム酸44ｇ／、コロイダルシリカ
8.3ｇ／
(サ) 無水クロム酸44ｇ／、コロイダルシリカ
16.5ｇ／
(シ) 無水クロム酸 ４ｇ／、コロイダルシリ
カ40ｇ／
(ス) 無水クロム酸 ４ｇ／、コロイダルシリ
カ55ｇ／
(セ) 無水クロム酸40ｇ／、コロイダルシリカ
５ｇ／、アクリルアミド樹脂0.8ｇ／
(ソ) 無水クロム酸44ｇ／、コロイダルシリカ
8.3ｇ／、アクリルアミド樹脂0.8ｇ／
(タ) 無水クロム酸44ｇ／、コロイダルシリカ
16.5ｇ／、アクリルアミド樹脂0.8ｇ／
(チ) 無水クロム酸４ｇ／、コロイダルシリカ40
ｇ／、アクリルアミド樹脂0.8ｇ／
(ツ) 無水クロム酸４ｇ／、コロイダルシリカ
55ｇ／、アクリルアミド樹脂0.8ｇ／
を含む水溶液に浸漬、ロール絞り後乾燥（130℃、
２分）して後、（ケ）〜（ス）についてはコロイ
ダルシリカ18ｇ／、りん酸10ｇ／の水溶液、
（セ）〜（ツ）についてはコロイダルシリカ18
ｇ／、アクリルアミド樹脂3.2ｇ／の水溶液
に浸漬、引き上げ後乾燥（130℃、２分）した。
この二層クロメート鋼板の特性を第２表に示
す。第２表より、第１層のSi／Crが0.1〜５が良
好な範囲であることがわかる。
実施例 ３
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
実施例１の(ク)に示す第一層形成処理液で処理、乾
燥後
(テ) アクリルアミド樹脂0.13ｇ／
(ト) アクリルアミド樹脂0.16ｇ／
(ナ) コロイダルシリカ0.4ｇ／、りん酸0.5
ｇ／、アクリルアミド樹脂0.07ｇ／
(ニ) コロイダルシリカ1.5ｇ／、アクリルアミ
ド樹脂1.6ｇ／
(ヌ) コロイダルシリカ1.8ｇ／、アクリルアミ
ド樹脂1.6ｇ／
(ネ) コロイダルシリカ180ｇ／、アクリルア
ミド樹脂1.6ｇ／
(ノ) コロイダルシリカ200ｇ／、アクリルア
ミド樹脂1.6ｇ／
(ハ) りん酸1.2ｇ／、アクリルアミド樹脂1.6
ｇ／
(ヒ) りん酸1.5ｇ／、アクリルアミド樹脂1.6
ｇ／
(フ) りん酸150ｇ／、アクリルアミド樹脂1.6
ｇ／
(ヘ) りん酸165ｇ／、アクリルアミド樹脂1.6
ｇ／
(ホ) コロイダルシリカ15ｇ／、りん酸135ｇ／
、アクリルアミド樹脂1.6ｇ／
(マ) コロイダルシリカ165ｇ／、りん酸12
ｇ／、アクリルアミド樹脂1.6ｇ／
(ミ) コロイダルシリカ165ｇ／、りん酸30
ｇ／、アクリルアミド樹脂1.6ｇ／
(ム) コロイダルシリカ36ｇ／、りん酸135
ｇ／、アクリルアミド樹脂1.6ｇ／
を含む第二層形成処理液で処理、乾燥した試料の
性能評価を第３表に示す。
これより、第二層が第一層の影響を受けずに表
層として機能するためには
Si＋Ｐ＋有機樹脂≧１（mg／m2）
であればよいことがわかる。
また、塗料一次密着性、塗料二次密着性、耐指
紋性のすべてを良好にするためには、第二層皮膜
中のSi、Ｐ、有機樹脂の量が、
Siを含むときはSi／（Ｐ＋有機樹脂）
＝0.1〜10P
を含むときはＰ／（Si＋有機樹脂）
＝0.1〜10
の範囲であればよいことがわかる。
実施例 ４
電気亜鉛めつき鋼板（亜鉛付着量20ｇ／m2）を
実施例１に示す(ク)の第一層形成処理液にて処理乾
燥後
(メ) りん酸7.5ｇ／、コロイダルシリカ８ｇ／
、アクリルアミド系樹脂0.8ｇ／、無水クロ
ム酸0.9ｇ／
(モ) りん酸7.5ｇ／、コロイダルシリカ８ｇ／
、アクリルアミド系樹脂0.8ｇ／、無水クロ
ム酸1.8ｇ／
(ヤ) りん酸7.5ｇ／、コロイダルシリカ８ｇ／
、アクリルアミド系樹脂0.8ｇ／、無水クロ
ム酸2.7ｇ／
(ユ) りん酸7.5ｇ／、コロイダルシリカ８ｇ／
、アクリルアミド系樹脂0.8ｇ／、無水クロ
ム酸４ｇ／
を含む第二層形成処理液中に浸漬、引き上げ、乾
燥した試料の性能評価結果を第４表に示す。
第４表より、第二層中のCr（Ｐ＋Si＋有機樹
脂）は0.2以下であることがよいことがわかる。
[Industrial Application Field] The present invention relates to a surface-treated steel sheet in which a chromate film is formed on a galvanized or zinc alloy-plated steel sheet. [Prior Art and its Problems] Conventionally, it is known that chromate treatment of galvanized steel sheets involves producing a film containing chromium as a main component and containing Si, P, and an organic resin. For example, Japanese Patent Publication No. 61-58552, Japanese Patent Publication No. 61-1508, which contain silica as Si,
There are those described in Japanese Patent Application Laid-Open No. 60-13079 and Japanese Patent Publication No. 61-54880. Furthermore, as P, phosphoric acid is added, as published in Japanese Patent Publication No. 53-41621, and as added with both Si and P, published in Japanese Patent Publication No. 60-41621.
There is one described in Publication No. 18751. These are traditional
The purpose is to further improve the corrosion resistance of a chromate film made only of Cr, as well as to provide better adhesion to paint. On the other hand, in recent years, steel sheets used for home appliances, office equipment, etc. are zinc or zinc-based alloy coated steel sheets, either unpainted or coated. In other words, the characteristics required for a steel plate include corrosion resistance and appearance (color tone, color unevenness) without painting, resistance to fingerprints during product manufacture and use, and adhesion to paint when painted. For a long time, chromate films formed by chromic acid treatment simply provided corrosion resistance, but as the various properties mentioned above became required, Si, P, and metal ions were added to the treatment solution. Furthermore, in order to improve the fingerprint resistance, organic resins have been added as shown in Japanese Patent Application Laid-Open No. 61-207579 and Japanese Patent Application Laid-Open No. 59-140050. However, it is difficult to meet all of the performance requirements in either case, and in particular, when forming processes such as bending and drawing are performed, the coating breaks down and the plating layer is exposed, causing white rust on the zinc from that area. It had the disadvantage that it was more likely to occur. (Problems to be Solved by the Invention) In view of the above points, the present invention provides corrosion resistance of chromate films on galvanized and zinc-based alloy coated steel sheets, corrosion resistance of processed parts, paint adhesion, fingerprint resistance, and color unevenness. The purpose of the present invention is to provide a chemical conversion treated steel sheet having a chromate film structure that improves all of the following. (Means for Solving the Problems) The above object can be advantageously achieved by forming a film having the structure shown below on a zinc or zinc-based alloy coated steel sheet. That is, the present invention provides a first layer on the surface of a zinc or zinc-based alloy plated steel sheet with Cr≧5mg/m 2 , Si≧3mg/m 2 , and Si/Cr=0.1.
It has a first layer film consisting of ~5, on which P,
Among Si and organic resins (water-soluble or water-dispersible),
Contains any two or more types, P + Si + organic resin ≧1
mg/m 2 and have a second layer film in the range of Si/(P + organic resin) = 0.1 to 10 when it contains Si, and P/(Si + organic resin) = 0.1 to 10 when it contains P. The gist is a chromate-treated steel sheet with excellent corrosion resistance in processed parts. It is also effective to contain Cr in the second layer in a range of Cr/(P+Si+organic resin)≦0.2. Furthermore, Cr in the second layer
Whether it includes or does not include,
It is also effective to include a water-soluble or water-dispersible organic resin in the first layer. The present invention will be explained in detail below. In constructing the present invention, the inventors conducted a detailed study on how the above-mentioned performances are affected by the film constituents. As a result Cr
Although effective for corrosion resistance, it tends to cause color unevenness, impairs the appearance, and is disadvantageous for paint adhesion and fingerprint resistance.Si is particularly effective for primary paint adhesion, but has a negative effect on secondary paint adhesion and fingerprint resistance. It has also been found that P has an advantage in corrosion resistance and anti-fingerprint properties, but is disadvantageous in primary paint adhesion. What is primary paint adhesion?
This refers to the adhesion between the paint and the surface of the steel plate immediately after the paint has been applied.
The evaluation was based on the number of peeled gobbles when a 10 x 10 incision was made and the adhesive tape was peeled off. (Goban tape method) Secondary paint adhesion refers to the paint adhesion after a painted steel plate is aged in a certain environment.In the present invention, after being kept in a 100% humidity tank for one week, This was evaluated using the goban tape method. Corrosion resistance of processed parts was evaluated using salt spray using test pieces bent at 180°.
It was found that those containing at least one type of Si are good, and those that do not contain both are very likely to cause white rust from the bent portions. In other words, Cr and Si are necessary to ensure corrosion resistance of the processed part. Organic resins have good effects on corrosion resistance, paint adhesion, and anti-fingerprint properties, but they are the most expensive compared to other constituent components, and it is not advantageous to contain them in large amounts. If we think carefully about the various performance details, we can see that corrosion resistance, color unevenness, etc. are the performance of the entire chromate film, while paint adhesion and fingerprint resistance are the performance of the outermost layer of the film. . In other words, the outermost layer has a structure that is advantageous for paint adhesion and fingerprint resistance.
If the inner layer has a structure with excellent corrosion resistance, it should be possible to satisfy all of the requirements of paint adhesion, fingerprint resistance, and corrosion resistance. It also tends to cause uneven coloring.
By restricting the Cr component to only the inner layer, that is, by removing it from the outermost layer, or by limiting its content to a small amount, problems in appearance can be solved. Based on this idea, the present invention requires that Cr and Si exist simultaneously in the first layer (lower layer). Both are effective for corrosion resistance, and Si is more effective for processed parts. Cr
When Si is less than 5 mg/m 2 and Si is less than 3 mg/m 2 , corrosion resistance is insufficient in both cases. Si/Cr is related to the corrosion resistance of the machined part, and if it is less than 0.1, the corrosion resistance of the machined part will be insufficient. Moreover, when Si/Cr exceeds 5, corrosion resistance in a salt spray test becomes poor. Furthermore, the inclusion of a water-soluble or water-dispersible organic resin in the first layer film has the effect of improving both the corrosion resistance of processed parts and the corrosion resistance of flat plates. The second layer (outer layer) is a layer whose purpose is to improve the primary paint adhesion, secondary paint adhesion, and fingerprint resistance, as well as to make the color unevenness and tone of the first layer uniform and colorless. The effects of resin, Si, and P on these performances are as follows. Although Si improves the primary adhesion of the paint, it reduces the secondary adhesion of the paint and fingerprint resistance. Although P reduces the primary adhesion of the paint, it helps maintain the secondary adhesion of the paint, and is effective in improving fingerprint resistance, reducing color unevenness in the first layer, making the color tone uniform, and making it colorless. The organic resin helps maintain the primary and secondary adhesion of the paint, and exhibits an improvement effect on fingerprint resistance when the amount added exceeds a certain level. Therefore, if at least two of organic resin, Si, and P are mixed to form a second layer film having a composition within the following range, the primary and secondary paint adhesion, fingerprint resistance, and uniform appearance can be improved. can improve everything. In order to make the color tone and color unevenness of the first layer uniform, it is necessary that (organic resin + P + Si) be 1 mg/m 2 or more, and if it is less than that, there is no effect. When containing Si, at least one of P and organic resin may be included in the second layer film in the range of Si/(P + organic resin)≦10 to alleviate the effect of Si on reducing secondary paint adhesion. On the other hand, in order not to impair the effect of Si on improving the primary adhesion of the paint, it is necessary that the upper limit of the amounts of P and organic resin be Si/(P+organic resin)≧0.1. When P is included, it is necessary to include at least one of Si and an organic resin in the second layer film in a range of P/(Si+organic resin)≦10 in order to alleviate the effect of P on reducing the primary adhesion of the paint. On the other hand, in order not to impair the fingerprint resistance improvement effect of P and the maintenance effect of secondary paint adhesion, the upper limit of the amount of Si and organic resin should be P/(Si+
organic resin) ≧0.1. Adding Cr is effective for uniform coating of the second layer film, but in order to maintain paint adhesion and fingerprint resistance, the amount of Cr added should be 1 to P + Si + organic resin in the second layer film. /10 or less, that is, Cr/(P+Si
+ organic resin) ≦0.2. As described in the above-mentioned patent publication, Cr can be easily included in the first layer forming treatment solution by dissolving chromic anhydride, chromate, and dichromate in water. It is possible to incorporate it into the film. At this time, a reducing agent is added to reduce Cr to trivalent, and the hexavalent in the first layer film is
There is no problem in increasing the ratio of trivalent Cr to Cr. Si can be easily obtained by dissolving or dispersing silica powder, colloidal silica, silane coupling agents, and various silicates in water, and P can be easily obtained by adding phosphoric acid, polyphosphoric acid, or phosphates to water. It is possible to create a layer forming treatment solution. All water-soluble or water-dispersible organic resins are applicable. To form a film on a steel plate, any film forming method commonly used for coated chromates can be applied, such as dipping-roll drawing-heat drying, roll coating, and spray coating. However, it is necessary to dry the first layer film after forming the first layer film and before forming the second layer film. Thereby, elution of the first layer in the second layer forming treatment liquid can be prevented. The chemical conversion treatment of the present invention can be applied to all steel sheets whose outermost layer is plated with zinc or zinc-based alloy. Galvanizing includes all galvanizing methods such as electrolytic galvanizing, hot-dip galvanizing, and vacuum evaporation galvanizing. Zinc-based alloy plating refers to all alloy plating containing zinc and one or more other metals, such as zinc-nickel, zinc-iron, and zinc-aluminum, as well as metal oxide plating such as silicon, titanium, aluminum, and chromium. This includes everything dispersed in the plating layer. Even in the case of having a plurality of plated layers, it is possible to apply the plated layer as long as the uppermost layer is the plated layer containing the above-mentioned zinc. Furthermore, it can be similarly applied to composite steel plates that are plated on one side or have a resin between them. Example 1 Electrogalvanized steel sheet (zinc coating amount 20 g/m 2 ) was coated with (a) chromic anhydride 2.7 g/m and colloidal silica.
10g/ (a) Chromic anhydride 4g/, colloidal silica
10g/ (U) Chromic anhydride 8.5g/, colloidal silica
10g/ (d) Chromic anhydride 4g/, colloidal silica
10g/, Acrylamide resin 0.8g/ (E) Chromic anhydride 8.5g/, Colloidal silica
1.8g/ (F) Chromic anhydride 8.5g/, colloidal silica 5g/ (G) Chromic anhydride 8.5g/, colloidal silica
1.8g/, acrylamide resin 0.8g/ (h) chromic anhydride 8.5g/, colloidal silica
Immerse in an aqueous solution containing 10 g/acrylamide resin, 0.8 g/acrylamide resin, roll squeeze, and dry (120
℃, 3 minutes) and post-phosphoric acid 3g/, colloidal silica 5g/, acrylamide resin 0.8g/,
Immersed in an aqueous solution containing
Table 1 shows the results of evaluating the characteristics of the double-layer chromate-treated steel sheet. From Table 1, it can be seen that in order to ensure corrosion resistance and corrosion resistance of processed parts, the first layer needs to contain 5 mg/m 2 or more of Cr and 3 mg/m 2 or more of Si. Example 2 Electrogalvanized steel sheet (zinc coating amount 20 g/m 2 ) (q) Chromic anhydride 40 g/, colloidal silica 5 g/ (q) chromic anhydride 44 g/, colloidal silica
8.3g/ (sa) Chromic anhydride 44g/, colloidal silica
16.5g/ (C) Chromic anhydride 4g/, Colloidal silica 40g/ (S) Chromic anhydride 4g/, Colloidal silica 55g/ (C) Chromic anhydride 40g/, Colloidal silica 5g/, Acrylamide resin 0.8g/ (S) ) Chromic anhydride 44g/, colloidal silica
8.3g/, Acrylamide resin 0.8g/ (T) Chromic anhydride 44g/, Colloidal silica
16.5g/, acrylamide resin 0.8g/ (h) Chromic anhydride 4g/, colloidal silica 40
g/, Acrylamide resin 0.8g/ (T) Chromic anhydride 4g/, Colloidal silica
55g/, immersed in an aqueous solution containing acrylamide resin 0.8g/, rolled and dried (130℃,
2 minutes), for (k) to (s), add an aqueous solution of colloidal silica 18g/, phosphoric acid 10g/,
Colloidal silica 18 for (C) to (T)
g/, immersed in an aqueous solution of 3.2 g/acrylamide resin, pulled up, and dried (130° C., 2 minutes). Table 2 shows the properties of this double layer chromate steel sheet. From Table 2, it can be seen that Si/Cr of the first layer is in a good range of 0.1 to 5. Example 3 An electrogalvanized steel sheet (zinc coating amount 20 g/m 2 ) was treated with the first layer forming treatment solution shown in (h) of Example 1, and after drying (te) acrylamide resin 0.13 g/(g) acrylamide Resin 0.16g/ (na) Colloidal silica 0.4g/, Phosphoric acid 0.5
g/, Acrylamide resin 0.07g/ (D) Colloidal silica 1.5g/, Acrylamide resin 1.6g/ (N) Colloidal silica 1.8g/, Acrylamide resin 1.6g/ (N) Colloidal silica 180g/, Acrylamide resin 1.6g/ ( (c) Colloidal silica 200g/, acrylamide resin 1.6g/ (c) Phosphoric acid 1.2g/, acrylamide resin 1.6
g/(H) Phosphoric acid 1.5g/, Acrylamide resin 1.6
g/ (F) Phosphoric acid 150g/, Acrylamide resin 1.6
g/ (F) Phosphoric acid 165g/, Acrylamide resin 1.6
g/ (e) Colloidal silica 15g/, phosphoric acid 135g/
, Acrylamide resin 1.6g/ (Ma) Colloidal silica 165g/, Phosphoric acid 12
g/, Acrylamide resin 1.6g/ (Mi) Colloidal silica 165g/, Phosphoric acid 30
g/, Acrylamide resin 1.6g/ (mu) Colloidal silica 36g/, Phosphoric acid 135
Table 3 shows the performance evaluation of the samples treated and dried with the second layer forming treatment solution containing 1.6 g/g/acrylamide resin and 1.6 g/acrylamide resin. From this, it can be seen that in order for the second layer to function as a surface layer without being influenced by the first layer, it is sufficient that Si+P+organic resin≧1 (mg/m 2 ). In addition, in order to improve primary paint adhesion, secondary paint adhesion, and anti-fingerprint properties, the amounts of Si, P, and organic resin in the second layer must be adjusted to Si/( It can be seen that when P/(Si+organic resin) = 0.1 to 10 P is included, the range of P/(Si + organic resin) = 0.1 to 10 is sufficient. Example 4 An electrogalvanized steel sheet (zinc adhesion amount: 20 g/m 2 ) was treated with the first layer forming treatment solution (h) shown in Example 1. After drying (h) 7.5 g of phosphoric acid, 8 g of colloidal silica. /
, Acrylamide resin 0.8g/, Chromic anhydride 0.9g/ (Mo) Phosphoric acid 7.5g/, Colloidal silica 8g/
, Acrylamide resin 0.8g/, Chromic anhydride 1.8g/ (Y) Phosphoric acid 7.5g/, Colloidal silica 8g/
, Acrylamide resin 0.8g/, Chromic anhydride 2.7g/ (y) Phosphoric acid 7.5g/, Colloidal silica 8g/
Table 4 shows the performance evaluation results of samples that were immersed in a second layer forming treatment solution containing 0.8 g/acrylamide resin and 4 g/chromic anhydride, pulled up, and dried. From Table 4, it can be seen that the content of Cr (P+Si+organic resin) in the second layer is preferably 0.2 or less.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
本発明は、耐食性を目的とする第一層と塗料密
着性および耐指紋性を目的とする第二層とに機能
を分離、分担させることにより耐食性、塗料密着
性、耐指紋性の全てにすぐれた性能を確保したも
のである。特に第一層にSiを３mg／m2以上含有す
ることによつて折り曲げなどの加工による加工部
の耐食性を向上させたクロメート処理鋼板を提供
する。
The present invention achieves excellent corrosion resistance, paint adhesion, and fingerprint resistance by separating and sharing the functions between the first layer, which aims at corrosion resistance, and the second layer, which aims at paint adhesion and fingerprint resistance. This ensures high performance. In particular, the present invention provides a chromate-treated steel sheet in which the corrosion resistance of processed parts such as bending is improved by containing 3 mg/m 2 or more of Si in the first layer.
Claims (1)
一層として、Cr≧５mg／m2、Si≧３mg／m2、Si／
Cr＝0.1〜５からなる第一層皮膜を有し、その上
にＰ、Si、有機樹脂（水溶性または水分散性）の
うち、いずれか２種以上を含み、Ｐ＋Si＋有機樹
脂≧１mg／m2、かつSiを含むときはSi／（Ｐ＋有
機樹脂）＝0.1〜10、Ｐを含むときはＰ／（Si＋有
機樹脂）＝0.1〜10の範囲にある第二層皮膜を有す
ることを特徴とする加工部耐食性の優れたクロメ
ート処理鋼板。 ２ 第二層中にCrをCr／（Ｐ＋Si＋有機樹脂）≦
0.2の範囲で含有することを特徴とする特許請求
の範囲第１項記載のクロメート処理鋼板。 ３ 第一層皮膜中に水溶性または水分散性有機樹
脂を含有せしめたことを特徴とする特許請求の範
囲第１項記載のクロメート処理鋼板。[Claims] 1. Cr≧5mg/m 2 , Si≧3mg/m 2 , Si/
It has a first layer film consisting of Cr = 0.1 to 5, and contains any two or more of P, Si, and organic resin (water-soluble or water-dispersible) on it, and P + Si + organic resin ≧ 1 mg / m 2 , and has a second layer film in the range of Si/(P+organic resin)=0.1 to 10 when containing Si, and P/(Si+organic resin)=0.1 to 10 when containing P. Chromate-treated steel sheet with excellent corrosion resistance in processed areas. 2 Cr in the second layer Cr/(P+Si+organic resin)≦
Chromate-treated steel sheet according to claim 1, characterized in that the content is in the range of 0.2. 3. The chromate-treated steel sheet according to claim 1, wherein the first layer film contains a water-soluble or water-dispersible organic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33275887A JPH01177377A (en) | 1987-12-30 | 1987-12-30 | Chromated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33275887A JPH01177377A (en) | 1987-12-30 | 1987-12-30 | Chromated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01177377A JPH01177377A (en) | 1989-07-13 |
| JPH0514789B2 true JPH0514789B2 (en) | 1993-02-25 |
Family
ID=18258516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33275887A Granted JPH01177377A (en) | 1987-12-30 | 1987-12-30 | Chromated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01177377A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58177476A (en) * | 1982-04-12 | 1983-10-18 | Kawasaki Steel Corp | Surface treatment of steel plate electroplated with zinc |
| JPS6050180A (en) * | 1983-08-31 | 1985-03-19 | Nippon Kokan Kk <Nkk> | Corrosion-preventive steel sheet for cationic electrodeposition painting |
| JPS6123872A (en) * | 1984-07-12 | 1986-02-01 | Nissan Motor Co Ltd | Knocking judging apparatus for internal-combustion engine |
| JPS6283478A (en) * | 1985-10-09 | 1987-04-16 | Sumitomo Metal Ind Ltd | Chromated steel material having superior adhesion to coating |
-
1987
- 1987-12-30 JP JP33275887A patent/JPH01177377A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58177476A (en) * | 1982-04-12 | 1983-10-18 | Kawasaki Steel Corp | Surface treatment of steel plate electroplated with zinc |
| JPS6050180A (en) * | 1983-08-31 | 1985-03-19 | Nippon Kokan Kk <Nkk> | Corrosion-preventive steel sheet for cationic electrodeposition painting |
| JPS6123872A (en) * | 1984-07-12 | 1986-02-01 | Nissan Motor Co Ltd | Knocking judging apparatus for internal-combustion engine |
| JPS6283478A (en) * | 1985-10-09 | 1987-04-16 | Sumitomo Metal Ind Ltd | Chromated steel material having superior adhesion to coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01177377A (en) | 1989-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4407899A (en) | Surface treated steel sheets for paint coating | |
| JPH0419313B2 (en) | ||
| GB2046312A (en) | Processes and compositions for coating metal surfaces | |
| US6720078B1 (en) | Organic composite coated zinc-based metal plated steel sheet | |
| JP4615807B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet | |
| JP3911160B2 (en) | Phosphate-treated galvanized steel sheet with excellent corrosion resistance and paintability | |
| US6294262B1 (en) | Composition and process for anticorrosive treatment of non-ferrous metal | |
| JP3923419B2 (en) | Non-chromium treatment of non-chromium steel sheet | |
| JP2002363764A (en) | Coating surface preparation agent, surface preparation method, metallic material, machining method and metallic product | |
| JPH11140665A (en) | Coated steel sheet excellent in edge face corrosion resistance and its production | |
| JPH0368115B2 (en) | ||
| JPH0514789B2 (en) | ||
| JPH09183186A (en) | Organically after-treated metal sheet | |
| US6071435A (en) | Composition and process for treating a zinciferous surface | |
| EP0553271B1 (en) | Preatment for zinc and zinc alloys prior to chromating | |
| KR960007775B1 (en) | Chromate solution of controlling an eruption of a chrome and the method for making c chromate steel plate using the same | |
| JPH0514790B2 (en) | ||
| JPH0541707B2 (en) | ||
| JP2959705B2 (en) | Phosphate treatment method for galvanized steel sheet | |
| JP3069027B2 (en) | White chromate treatment with excellent chromium elution resistance, corrosion resistance and coating performance | |
| JPH0432576A (en) | Solution for zinc phosphate chemical conversion treatment | |
| JPH07300683A (en) | Chromating method excellent in low-temperature baking property | |
| JP3600759B2 (en) | Phosphate-treated galvanized steel sheet excellent in workability and method for producing the same | |
| KR100509183B1 (en) | Zinc phosphate-treated galvanized steel sheet excellent in corrosion resistance and color tone | |
| JP3156580B2 (en) | Manufacturing method of galvanized steel sheet with excellent white rust resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |