JPH0564237B2 - - Google Patents
Info
- Publication number
- JPH0564237B2 JPH0564237B2 JP2079586A JP2079586A JPH0564237B2 JP H0564237 B2 JPH0564237 B2 JP H0564237B2 JP 2079586 A JP2079586 A JP 2079586A JP 2079586 A JP2079586 A JP 2079586A JP H0564237 B2 JPH0564237 B2 JP H0564237B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- single layer
- layers
- blackening treatment
- zinc
- 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
- 229910000831 Steel Inorganic materials 0.000 claims description 28
- 239000010959 steel Substances 0.000 claims description 28
- 239000010410 layer Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002356 single layer Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 235000005985 organic acids Nutrition 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 11
- 229910000990 Ni alloy Inorganic materials 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910007567 Zn-Ni Inorganic materials 0.000 description 7
- 229910007614 Zn—Ni Inorganic materials 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000003839 salts Chemical class 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- -1 for example Polymers 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008859 change Effects 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
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching 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
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Description
［産業上の利用分野］
本発明は黒色亜鉛めつき鋼板の保護皮膜製造法
に関し、より詳しくは、亜鉛合金めつき鋼板に黒
色化処理を施したのちに、加工性及び耐食性にす
ぐれた保護皮膜を形成せしめる黒色亜鉛めつき鋼
板の保護皮膜製造法に関する。
［従来の技術］
従来、装飾性、光吸収性、吸熱性あるいは光反
射防止性を向上させた黒色化鋼板は、家電製品の
シヤーシ類や複写器の光学系の周辺部品に数多く
利用されてきた。
しかし近年、コスト低減の目的から、加工後に
塗装を行なうという従来の黒色化方法から、あら
かじめ黒色化された亜鉛合金めつき鋼板を使用す
る方法に代わりつつある。
このようにあらかじめ黒色化する場合には、黒
色化後加工を行なうことになるので、かかる鋼板
にはすぐれた加工性が要求される。
また、黒色化されためつき鋼板は、それ自体耐
摩耗性に乏しく、非常に傷つき易く黒色化皮膜の
美感が著しくそこなわれやすい。そして、傷部か
ら発錆し、発錆すると、白色の腐食精製物を生成
し、緻密美麗な外観が損なわれる。
黒色化された亜鉛合金めつき鋼板に皮膜を形成
させたものとしては、表面に、陽極電解処理を程
こしたものが知られている（特開昭58−154190号
公報）。
［発明が解決しようとする問題点］
（発明が解決しようとする問題点）
特開昭58−151490号公報に開示された技術にお
いても、耐摩耗性を十分には向上させることがで
きず、従来技術で述べたような発錆が生じ、緻密
な外観が損なわれるという問題は解決されていな
い。
また、黒色化された亜鉛合金めつき鋼板は加工
時には表面の黒色化層が一層傷つき易く、加工後
に塩水噴霧試験（JIS2371）により耐食性を調べ
ると白錆が発生し、緻密な黒色化表面が損なわれ
てしまう。
［問題点を解決するための技術的手段］
本出願に係る第１発明は、Ni，Co又はMoの１
種以上をNi，Coについて0.5〜30wt％、Moにつ
いて0.5〜10wt％含有する亜鉛を主成分とする亜
鉛合金のめつき層を単層あるいは２層以上有する
鋼板を、塩酸、硫酸、有機酸の一種または二種以
上を合計で0.1〜20wt％を含有し、かつ過酸化水
素水0.1〜20wt％を含有する黒色化処理液により
黒色化処理し、次いで、黒色化処理した該鋼板の
表面に塗付型クロメート皮膜を単層又は２層以上
形成せしめることを特徴とする黒色亜鉛めつき鋼
板の保護皮膜製造法をその要旨とする。
本出願に係る第２発明は、Ni，Co又はMoの１
種以上をNi，Coについて0.5〜30wt％、Moにつ
いて0.5〜10wt％含有する亜鉛を主成分とする亜
鉛合金のめつき層を単層あるいは２層以上有する
鋼板を、塩酸、硫酸、有機酸の一種または二種以
上を合計で0.1〜20wt％を含有し、かつ過酸化水
素水0.1〜20wt％を含有する黒色化処理液により
黒色化処理し、次いで、黒色化処理した該鋼板の
表面にケイ酸コロイド、水ガラス、シランカツプ
リング剤、有機樹脂、水性樹脂、無水クロム酸の
うち１種あるいは２種以上を含んだ溶液を塗付・
乾燥して皮膜を単層あるいは２層以上形成せしめ
ることを特徴とする黒色亜鉛めつき鋼板の保護皮
膜製造法をその要旨とする。
本出願に係る第３発明は、Ni，Co又はMoの１
種以上をNi，Coについて0.5〜30wt％、Moにつ
いて0.5〜10wt％含有する亜鉛を主成分とする亜
鉛合金のめつき層を単層あるいは２層以上有する
鋼板を、塩酸、硫酸、有機酸の一種または二種以
上を合計で0.1〜20wt％を含有し、かつ過酸化水
素水0.1〜20wt％を含有する黒色化処理液により
黒色化処理し、次いで、黒色化処理した該鋼板の
表面に塗付型クロメート皮膜を単層又は２層以上
形成せしめ、さらに、該クロメート皮膜上に、ケ
イ酸コロイド、水ガラス、シランカツプリング
酸、有機樹脂、水性樹脂、無水クロム酸のうち１
種あるいは２種以上を含んだ溶液を塗付・乾燥し
て皮膜を単層あるいは２層以上形成せしめること
を特徴とする黒色亜鉛めつき鋼板の保護皮膜製造
法をその要旨とする。
（第１発明）
第１発明においては、塩酸、硫酸、有機酸（カ
ルボン酸）の一種または二種以上の濃度は合計
で、0.1〜20wt％とするのは、0.1wt％未満では、
適当な処理時間（２〜３分以内）内では黒色化し
ないからであり、また、20wt％を越えると黒色
化反応が速くなり反応をコントロールできなくな
るからである。
一方、本発明では、塩酸、硫酸、有機酸（カル
ボン酸）の一種または二種以上のほかに過酸化水
素水を用いる。
過酸化水素水の濃度は、0.1〜20wt％とする。
0.1wt％未満では、適当な処理時間（２〜３分以
内）内では黒色化しない。また、20wt％を越え
ると黒色化反応が速くなり反応をコントロールで
きなくなる。
このように、塩酸、硫酸、有機酸（カルボン
酸）の一種または二種以上のほかに過酸化水素水
を用いる場合には、耐食性を損なうことなく黒色
化反応を速やかに進行させることが可能となる。
すなわち、硝酸などの酸の単独使用の場合におい
ては、酸としての作用と酸化剤としての作用をあ
わせもつため亜鉛めつき層を溶解してしまいやす
く、ひどい場合には下地の鉄を露出させてしま
い、耐食性の劣化をまねきやすい。
しかるに、塩酸、硫酸、有機酸（カルボン酸）
の一種または二種以上のほかに過酸化水素水をそ
れぞれ所定の濃度で含有せしめて用いる場合に
は、それぞれを独立に制御することができるため
亜鉛めつき層の溶解を生ずることなく黒色化反応
を速めることができる。
なお、黒色化処理は、たとえば、浸漬、スプレ
ー吹付等によればよい。
第１発明においては、黒色化処理後塗布型クロ
メート皮膜を単層又は２層以上形成する。ここ
で、塗付型クロメート皮膜とは、クロム酸、ケイ
酸化合物及び微量添加剤を含有した溶液を塗付・
乾燥して得られる皮膜であり、めつき表面をエツ
チングしながらクロメート皮膜を形成するという
従来の反応型クロメート皮膜とは異なる。
なお、皮膜は、皮膜量0.01ｇ〜１ｇ／m2の範囲
内で塗付することが好ましい。
（第２発明）
黒色化処理に用いる酸、酸化剤の種類及びこれ
らの濃度については第１発明で述べたと同様であ
る。
本発明においては、黒色化処理した該鋼板の表
面にケイ酸コロイド、水ガラス、シランカツプリ
ング剤、有機樹脂、水性樹脂、無水クロム酸のう
ち１種あるいは２種以上を含んだ溶液を塗付・乾
燥して皮膜を単層あるいは２層以上形成せしめ
る。
かかる層の形成手段については特に限定しない
が、無水クロム酸、コロイダルシリカ、リン酸を
含有した溶液を、皮膜量を0.01ｇ〜１ｇ／m2の範
囲内で塗付することが好ましい。
有機樹脂としては、例えばエポキシ樹脂、アク
リル樹脂、メラミン樹脂、フエノール樹脂、尿素
樹脂等を用いればよい。
水性樹脂は、エマルジヨン型の樹脂を示し、た
とえば、アクリル−スチレン、エポキシエステ
ル、アクリル、ポリ酢酸ビニル、ポリスエチレ
ン、エチレン−酢酸ビニル、コポリマー系のエマ
ルジヨン樹脂等を用いればよい。
（第３発明）
すなわち、第３発明においては、まず、第１発
明で述べた皮膜を形成後、該皮膜上に第２発明で
述べた皮膜を形成せしめるものである。
なお、塩酸、硫酸、有機酸の一種または二種以
上を合計で0.1〜20wt％を含有し、かつ過酸化水
素水0.1〜20wt％を含有する黒色化処理液により
黒色化処理した黒色化層への上記皮膜の付着性は
従来解明されていないが、後述する実施例の耐食
性試験の結果、耐食性に優れていることが確認さ
れていることからして、付着性は良好であること
を確認した。
［発明の実施例］
（第１発明の実施例）
〈実施例 11〉
Zn−Ni合金めつき（Ni含有率12wt％）30ｇ／
m2を施した鋼板につき、酸及び酸化剤（過酸化水
素水およびクエン酸）の混合溶液中で浸漬処理を
おこなうことにより黒色化処理をした。
次いで、黒色化したZn−Niめつき鋼板上に、
塗付型クロメート溶液（無水クロム酸、コロイダ
ルシリカ、リン酸の混合溶液）をクロム付着量が
100ｇ／m2塗付となる厚さに塗付・乾燥した。
（第２発明の実施例）
〈実施例 21〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理し、シランカツプリング剤（信越化
学社製）を塗付したのちロール絞りを行つた。皮
膜厚さ１ｇ／m2とした。
〈実施例 22〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、ケイ酸コロイド（日産化
学社製）と水ガラス３号を重量比で８：２の割合
で混合した溶液を、黒色化したZn−Niめつき鋼
板上に塗付・乾燥した。皮膜付着量２ｇ／m2とし
た。
〈実施例 23〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、無水クロム酸と水性アク
リルエマルジヨンを１：10の比率で混合し、黒色
化したZn−Niめつき鋼板に塗付したのちロール
絞りを行ない、乾燥した。皮膜付着量は３ｇ／m2
とした。
〈実施例 24〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、水性アクリルエマルジヨ
ンを、黒色化したZn−Niめつき鋼板上に塗付ロ
ール絞りを施したのち乾燥し、皮膜付着量は５
ｇ／m2とした。
〈実施例 25〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、水性アクリルエマルジヨ
ン：コロイダルシリカ：シランカツプリング剤を
重量比で12：20：１の比率で混合し、黒色化した
Zn−Niめつき鋼板上に塗付したのちロール絞り、
乾燥をおこなつた。
〈実施例 26〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、水性アクリルエマルジヨ
ンを黒色化したZn−Niめつき鋼板上に塗付、乾
燥した。皮膜付着量３ｇ／m2とした。
（第３発明の実施例）
〈実施例 31〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、第１層として塗付クロメ
ート（無水クロム酸、コロイダルシリカ、リン
酸）をクロム付着量が100ｇ／m2となる厚さ塗
付・乾燥後、第２層としてケイ酸コロイド（日産
化学社製）と水ガラス３号を重量比で８：２の割
合で混合した溶液を塗布・乾燥した。皮膜は、付
着量２ｇ／m2とした。
〈実施例 32〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理したのち、第１層として塗付型クロ
メート（無水クロム酸、コロイダルシリカ、リン
酸）を、クロム付着量が100ｇ／m2となるよう塗
付したのち、シリカンカツプリング剤を１ｇ／m2
塗付、乾燥後、水性アクリルエマルジヨンを１〜
２ｇ／m2塗付・乾燥した。
〈比較例 １〉
第１実施例と同様に亜鉛−ニツケル合金めつき
を黒色化処理した。保護皮膜は施こさなかつた
（無処理）。
（各種試験）
以上のようにして皮膜を形成した黒色亜鉛めつ
き鋼板につき次の項目の試験を行なつた。
黒色度
黒色度は色差計（スガ試験機社製）により測定
した。Ｌ値は小さい程黒色度が良好であることを
示す。
外観の均一性
外観の均一性は目視により観察した。
耐食性
耐食性は、塩水噴霧試験（JIS2371）に基づき
５％塩水にて行ない、白錆発生までの時間を測定
した。
加工後の黒色度
90°の曲げ加工を行ない、加工後の黒色度の変
化を目視により測定した。
以上の結果をまとめて第１表に示す。
第１表に示すように、実施例における加工前の
黒色度は比較例に比べ遜色はない。しかし、実施
例においては、加工後の黒色度、外観の均一性、
耐食性はいずれも比較例に比べ優れている。特に
実施例12〜15については、外観の均一性は著しく
優れている。
［発明の効果］
本出願に係る第１発明から第３発明によれば、
耐摩耗性に優れ、黒色化皮膜の美感を損なうこと
なく、また、発錆することなく、緻密美麗な外観
が損なうことのない黒色亜鉛めつき鋼板を得るこ
とができる。
また、着色化処理過程で表面に発生した微妙な
色調ムラが消失し、均一な表面色調が得られる。
すなわち、着色層上に透明あるいは半透明層が塗
布されることにより光の屈折率が変化し、黒色表
面の均一性が向上する。
[Field of Industrial Application] The present invention relates to a method for producing a protective coating for a black galvanized steel sheet, and more specifically, a method for producing a protective coating with excellent workability and corrosion resistance after blackening a zinc alloy coated steel sheet. This invention relates to a method for producing a protective film on a black galvanized steel sheet. [Prior art] Blackened steel sheets with improved decorative properties, light absorption, heat absorption, or antireflection properties have been widely used in chassis of home appliances and peripheral parts of optical systems of copiers. . However, in recent years, for the purpose of cost reduction, the conventional blackening method of painting after processing is being replaced by a method of using zinc alloy plated steel sheets that have been blackened in advance. In the case where the steel sheet is blackened in advance in this manner, processing is performed after blackening, and therefore, such a steel sheet is required to have excellent workability. Further, the blackened and glazed steel sheet itself has poor wear resistance and is very easily damaged, so that the aesthetic appearance of the blackened coating is likely to be significantly impaired. Then, rust develops from the scratched part, and when it rusts, a white corrosive product is produced, which spoils the fine and beautiful appearance. As a blackened zinc alloy coated steel sheet on which a film is formed, one that has been subjected to anodic electrolytic treatment on the surface is known (Japanese Patent Application Laid-open No. 154190/1983). [Problems to be solved by the invention] (Problems to be solved by the invention) Even with the technique disclosed in JP-A-58-151490, wear resistance cannot be sufficiently improved. The problem of rust occurring and the fine appearance being impaired as described in the prior art has not been solved. In addition, the blackened layer on the surface of blackened zinc alloy coated steel sheets is more easily damaged during processing, and when the corrosion resistance is examined by a salt spray test (JIS2371) after processing, white rust occurs and the dense blackened surface is damaged. It gets lost. [Technical means for solving the problem] The first invention according to the present application is a method for solving the problem by
A steel plate having a single or two or more plating layers of a zinc alloy mainly composed of zinc containing 0.5 to 30 wt% of Ni and Co and 0.5 to 10 wt% of Mo is treated with hydrochloric acid, sulfuric acid, and organic acids. A blackening treatment is performed using a blackening treatment solution containing a total of 0.1 to 20 wt% of one or more types and 0.1 to 20 wt% of a hydrogen peroxide solution, and then coating on the surface of the blackened steel sheet. The gist of the present invention is a method for producing a protective film for a black galvanized steel sheet, which is characterized by forming a molded chromate film in a single layer or in two or more layers. The second invention according to the present application is one of Ni, Co or Mo.
A steel plate having a single or two or more plating layers of a zinc alloy mainly composed of zinc containing 0.5 to 30 wt% of Ni and Co and 0.5 to 10 wt% of Mo is treated with hydrochloric acid, sulfuric acid, and organic acids. A blackening treatment is carried out using a blackening treatment solution containing one or more types in a total amount of 0.1 to 20 wt% and a hydrogen peroxide solution of 0.1 to 20 wt%, and then silicon is applied to the surface of the blackened steel sheet. Apply a solution containing one or more of acid colloid, water glass, silane coupling agent, organic resin, aqueous resin, and chromic anhydride.
The gist of this invention is a method for producing a protective coating on a black galvanized steel sheet, which is characterized by drying to form a single layer or two or more layers of the coating. The third invention according to the present application is one of Ni, Co or Mo.
A steel plate having a single or two or more plating layers of a zinc alloy mainly composed of zinc containing 0.5 to 30 wt% of Ni and Co and 0.5 to 10 wt% of Mo is treated with hydrochloric acid, sulfuric acid, and organic acids. A blackening treatment is performed using a blackening treatment solution containing a total of 0.1 to 20 wt% of one or more types and 0.1 to 20 wt% of a hydrogen peroxide solution, and then coating on the surface of the blackened steel sheet. A molded chromate film is formed in a single layer or two or more layers, and one of silicic acid colloid, water glass, silane coupling acid, organic resin, aqueous resin, and chromic anhydride is further added on the chromate film.
The gist of this invention is a method for producing a protective coating for a black galvanized steel sheet, which is characterized by forming a single layer or two or more layers of coating by applying and drying a solution containing one or more species. (First invention) In the first invention, the total concentration of one or more types of hydrochloric acid, sulfuric acid, and organic acids (carboxylic acids) is 0.1 to 20 wt%, but if it is less than 0.1 wt%,
This is because blackening does not occur within an appropriate treatment time (within 2 to 3 minutes), and if the amount exceeds 20 wt%, the blackening reaction becomes too rapid to be controlled. On the other hand, in the present invention, a hydrogen peroxide solution is used in addition to one or more of hydrochloric acid, sulfuric acid, and organic acids (carboxylic acids). The concentration of hydrogen peroxide solution is 0.1 to 20 wt%.
If the amount is less than 0.1 wt%, blackening will not occur within an appropriate processing time (within 2 to 3 minutes). Moreover, if the amount exceeds 20 wt%, the blackening reaction becomes faster and the reaction cannot be controlled. In this way, when hydrogen peroxide is used in addition to one or more of hydrochloric acid, sulfuric acid, and organic acids (carboxylic acids), it is possible to rapidly advance the blackening reaction without impairing corrosion resistance. Become.
In other words, when an acid such as nitric acid is used alone, it has both the action of an acid and the action of an oxidizing agent, so it tends to dissolve the galvanized layer, and in severe cases, it can expose the underlying iron. This can easily lead to deterioration of corrosion resistance. However, hydrochloric acid, sulfuric acid, organic acids (carboxylic acids)
When hydrogen peroxide is used in addition to one or more of the following at a predetermined concentration, each can be controlled independently and the blackening reaction can be carried out without dissolving the galvanized layer. can be accelerated. Note that the blackening treatment may be performed by, for example, dipping, spraying, or the like. In the first invention, a coated chromate film is formed in a single layer or in two or more layers after the blackening treatment. Here, the paint-on type chromate film refers to the application of a solution containing chromic acid, silicic acid compounds, and trace additives.
This film is obtained by drying, and is different from conventional reactive chromate films in which a chromate film is formed by etching the plated surface. The coating is preferably applied in an amount of 0.01 g to 1 g/m 2 . (Second invention) The types and concentrations of acids and oxidizing agents used in the blackening treatment are the same as those described in the first invention. In the present invention, a solution containing one or more of silicic acid colloid, water glass, silane coupling agent, organic resin, aqueous resin, and chromic anhydride is applied to the surface of the blackened steel sheet.・Dry to form a single layer or two or more layers. Although there are no particular limitations on the means for forming such a layer, it is preferable to apply a solution containing chromic anhydride, colloidal silica, and phosphoric acid in a coating amount within the range of 0.01 g to 1 g/m 2 . As the organic resin, for example, epoxy resin, acrylic resin, melamine resin, phenolic resin, urea resin, etc. may be used. The aqueous resin is an emulsion type resin, and for example, acrylic-styrene, epoxy ester, acrylic, polyvinyl acetate, polyethylene, ethylene-vinyl acetate, copolymer emulsion resin, etc. may be used. (Third invention) That is, in the third invention, first, the film described in the first invention is formed, and then the film described in the second invention is formed on the film. In addition, the blackening layer is treated with a blackening treatment liquid containing a total of 0.1 to 20 wt% of one or more of hydrochloric acid, sulfuric acid, and organic acids and 0.1 to 20 wt% of hydrogen peroxide. Although the adhesion of the above-mentioned film has not been elucidated to date, it has been confirmed that the adhesion is good, as it has been confirmed that it has excellent corrosion resistance as a result of the corrosion resistance test in the example described below. . [Embodiments of the invention] (Embodiments of the first invention) <Example 11> Zn-Ni alloy plating (Ni content 12wt%) 30g/
A steel plate subjected to m 2 was subjected to a blackening treatment by immersion treatment in a mixed solution of an acid and an oxidizing agent (hydrogen peroxide and citric acid). Next, on the blackened Zn-Ni plated steel plate,
Apply a coating type chromate solution (a mixed solution of chromic anhydride, colloidal silica, and phosphoric acid) to
It was applied and dried to a thickness of 100g/ m2 . (Example of the second invention) <Example 21> As in the first example, the zinc-nickel alloy plating was treated to blacken, and a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied, followed by roll drawing. I went. The film thickness was 1 g/m 2 . <Example 22> After blackening the zinc-nickel alloy plating in the same manner as in the first example, silicate colloid (manufactured by Nissan Chemical Co., Ltd.) and water glass No. 3 were mixed at a weight ratio of 8:2. The solution was applied onto a blackened Zn-Ni plated steel plate and dried. The amount of film deposited was 2 g/m 2 . <Example 23> After blackening the zinc-nickel alloy plating in the same manner as in the first example, a blackened Zn-Ni plate was prepared by mixing chromic anhydride and aqueous acrylic emulsion at a ratio of 1:10. After applying it to a steel plate, it was rolled and dried. Film adhesion amount is 3g/m 2
And so. <Example 24> After blackening the zinc-nickel alloy plating in the same manner as in the first example, a water-based acrylic emulsion was applied on the blackened Zn-Ni plated steel plate, and then rolled and squeezed. After drying, the film adhesion amount is 5.
g/ m2 . <Example 25> After blackening the zinc-nickel alloy plating in the same manner as in the first example, aqueous acrylic emulsion: colloidal silica: silane coupling agent was mixed in a weight ratio of 12:20:1. and turned black
After coating on Zn-Ni plated steel plate, roll drawing,
I did some drying. <Example 26> After blackening the zinc-nickel alloy plating in the same manner as in the first example, an aqueous acrylic emulsion was applied onto the blackened Zn-Ni plated steel plate and dried. The amount of film deposited was 3 g/m 2 . (Example of the third invention) <Example 31> After blackening the zinc-nickel alloy plating in the same manner as in the first example, a coating of chromate (chromic anhydride, colloidal silica, phosphoric acid) was applied as the first layer. ) was applied to a thickness such that the amount of chromium deposited was 100 g/m 2 and dried, and as a second layer, silicate colloid (manufactured by Nissan Chemical Co., Ltd.) and water glass No. 3 were mixed at a weight ratio of 8:2. The solution was applied and dried. The coating had a coating weight of 2 g/m 2 . <Example 32> After blackening the zinc-nickel alloy plating in the same manner as in the first example, a coating type chromate (chromic anhydride, colloidal silica, phosphoric acid) was applied as the first layer, and the amount of chromium deposited was After applying to 100g/ m2 , apply 1g/ m2 of silicone coupling agent.
After application and drying, apply 1~1 water-based acrylic emulsion.
2 g/m 2 was applied and dried. <Comparative Example 1> Zinc-nickel alloy plating was subjected to blackening treatment in the same manner as in the first example. No protective film was applied (no treatment). (Various Tests) The following tests were conducted on the black galvanized steel sheet on which the film was formed as described above. Blackness Blackness was measured using a color difference meter (manufactured by Suga Test Instruments Co., Ltd.). The smaller the L value, the better the blackness. Uniformity of appearance Uniformity of appearance was visually observed. Corrosion Resistance Corrosion resistance was tested in 5% salt water based on the salt spray test (JIS2371), and the time until white rust appeared was measured. Blackness after processing A bending process of 90° was performed, and the change in blackness after processing was visually measured. The above results are summarized in Table 1. As shown in Table 1, the degree of blackness before processing in the examples is comparable to that in the comparative examples. However, in the examples, the degree of blackness after processing, uniformity of appearance,
Corrosion resistance is superior to that of the comparative examples. Especially for Examples 12 to 15, the uniformity of appearance is extremely excellent. [Effect of the invention] According to the first to third inventions of the present application,
It is possible to obtain a black galvanized steel sheet that has excellent wear resistance, does not impair the aesthetic appearance of the blackened coating, does not rust, and does not impair its dense and beautiful appearance. In addition, subtle color unevenness that occurs on the surface during the coloring process disappears, and a uniform surface color can be obtained.
That is, by coating a transparent or semitransparent layer on the colored layer, the refractive index of light changes and the uniformity of the black surface improves.
【表】【table】
【表】【table】
Claims (1)
て0.5〜30wt％、Moについて0.5〜10wt％含有す
る亜鉛を主成分とする亜鉛合金のめつき層を単層
あるいは２層以上有する鋼板を、塩酸、硫酸、有
機酸の一種または二種以上を合計で0.1〜20wt％
を含有し、かつ過酸化水素水0.1〜20wt％を含有
する黒色化処理液により黒色化処理し、次いで、
黒色化処理した該鋼板の表面に塗付型クロメート
皮膜を単層又は２層以上形成せしめることを特徴
とする黒色亜鉛めつき鋼板の保護皮膜製造法。 ２ Ni，Co又はMoの１種以上をNi，Coについ
て0.5〜30wt％、Moについて0.5〜10wt％含有す
る亜鉛を主成分とする亜鉛合金のめつき層を単層
あるいは２層以上有する鋼板を、塩酸、硫酸、有
機酸の一種または二種以上を合計で0.1〜20wt％
を含有し、かつ過酸化水素水0.1〜20wt％を含有
する黒色化処理液により黒色化処理し、次いで、
黒色化処理した該鋼板の表面にケイ酸コロイド、
水ガラス、シランカツプリング剤、有機樹脂、水
性樹脂、無水クロム酸のうち１種あるいは２種以
上を含んだ溶液を塗付・乾燥して皮膜を単層ある
いは２層以上形成せしめることを特徴とする黒色
亜鉛めつき鋼板の保護皮膜製造法。 ３ Ni，Co又はMoの１種以上をNi，Coについ
て0.5〜30wt％、Moについて0.5〜10wt％含有す
る亜鉛を主成分とする亜鉛合金のめつき層を単層
あるいは２層以上有する鋼板を、塩酸、硫酸、有
機酸の一種または二種以上を合計で0.1〜20wt％
を含有し、かつ過酸化水素水0.1〜20wt％を含有
する黒色化処理液により黒色化処理し、次いで、
黒色化処理した該鋼板の表面に塗付型クロメート
皮膜を単層又は２層以上形成せしめ、さらに、該
クロメート皮膜上に、ケイ酸コロイド、水ガラ
ス、シランカツプリング酸、有機樹脂、水性樹
脂、無水クロム酸のうち１種あるいは２種以上を
含んだ溶液を塗付・乾燥して皮膜を単層あるいは
２層以上形成せしめることを特徴とする黒色亜鉛
めつき鋼板の保護皮膜製造法。[Claims] 1. A single layer or a plated layer of a zinc alloy mainly composed of zinc containing one or more of Ni, Co, or Mo at 0.5 to 30 wt% for Ni and Co and 0.5 to 10 wt% for Mo. A steel plate with two or more layers is treated with one or more types of hydrochloric acid, sulfuric acid, and organic acids in a total of 0.1 to 20 wt%.
and blackening treatment with a blackening treatment solution containing 0.1 to 20 wt% hydrogen peroxide solution, and then
A method for producing a protective film for a black galvanized steel sheet, which comprises forming a single layer or two or more layers of a painted chromate film on the surface of the blackened steel sheet. 2. A steel sheet having a single layer or two or more plating layers of a zinc alloy whose main component is zinc containing one or more of Ni, Co, or Mo, 0.5 to 30 wt% for Ni and Co, and 0.5 to 10 wt% for Mo. , hydrochloric acid, sulfuric acid, and one or more organic acids, totaling 0.1 to 20 wt%
and blackening treatment with a blackening treatment solution containing 0.1 to 20 wt% hydrogen peroxide solution, and then
Silicic acid colloid is applied to the surface of the blackened steel sheet.
A film is formed by applying and drying a solution containing one or more of water glass, silane coupling agent, organic resin, aqueous resin, and chromic anhydride to form a single layer or two or more layers. A method for manufacturing a protective film on black galvanized steel sheets. 3 A steel sheet having a single layer or two or more plating layers of a zinc alloy whose main component is zinc containing one or more of Ni, Co, or Mo, 0.5 to 30 wt% for Ni and Co, and 0.5 to 10 wt% for Mo. , hydrochloric acid, sulfuric acid, and one or more organic acids, totaling 0.1 to 20 wt%
and blackening treatment with a blackening treatment solution containing 0.1 to 20 wt% hydrogen peroxide solution, and then
A coating type chromate film is formed in a single layer or two or more layers on the surface of the blackened steel sheet, and further, on the chromate film, silicic acid colloid, water glass, silane coupling acid, organic resin, aqueous resin, A method for producing a protective film for a black galvanized steel sheet, which comprises applying and drying a solution containing one or more of chromic anhydride to form a single layer or two or more layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2079586A JPS62180080A (en) | 1986-01-31 | 1986-01-31 | Production of protective film for black galvanized steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2079586A JPS62180080A (en) | 1986-01-31 | 1986-01-31 | Production of protective film for black galvanized steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62180080A JPS62180080A (en) | 1987-08-07 |
| JPH0564237B2 true JPH0564237B2 (en) | 1993-09-14 |
Family
ID=12037000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2079586A Granted JPS62180080A (en) | 1986-01-31 | 1986-01-31 | Production of protective film for black galvanized steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62180080A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062389B2 (en) * | 1990-05-30 | 1994-01-12 | 新日本製鐵株式会社 | Organic / inorganic composite steel sheet with excellent heat resistance, heat discoloration resistance, and corrosion resistance |
| WO2001012877A1 (en) * | 1998-08-18 | 2001-02-22 | Walter Hillebrand Gmbh & Co. Galvanotechnik | Passivation method for zinc-nickel layers |
| BR9913088A (en) * | 1998-08-18 | 2001-05-08 | Walter Hillebrand Gmbh & Co Ga | Coating system |
| DE19905134A1 (en) * | 1999-02-09 | 2000-09-28 | Hillebrand Walter Gmbh & Co Kg | Passivation process |
| KR100498093B1 (en) * | 2000-11-28 | 2005-07-01 | 주식회사 포스코 | A blackening treatment steel sheet with good surface appearence, and a blackening treatment solution |
| JP5149503B2 (en) * | 2006-12-08 | 2013-02-20 | 株式会社Ｊｃｕ | Metal blackening treatment liquid, metal blackening treatment method using the metal blackening treatment liquid, and blackening treatment product using the metal blackening treatment method |
| JP6571198B2 (en) * | 2016-03-22 | 2019-09-04 | 奥野製薬工業株式会社 | Film-forming composition and method for treating metal material |
-
1986
- 1986-01-31 JP JP2079586A patent/JPS62180080A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62180080A (en) | 1987-08-07 |
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