JPH0340116B2 - - Google Patents
Info
- Publication number
- JPH0340116B2 JPH0340116B2 JP61192613A JP19261386A JPH0340116B2 JP H0340116 B2 JPH0340116 B2 JP H0340116B2 JP 61192613 A JP61192613 A JP 61192613A JP 19261386 A JP19261386 A JP 19261386A JP H0340116 B2 JPH0340116 B2 JP H0340116B2
- Authority
- JP
- Japan
- Prior art keywords
- colored
- zinc
- coating
- plating
- clo
- 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
- 239000011701 zinc Substances 0.000 claims description 50
- 229910000831 Steel Inorganic materials 0.000 claims description 43
- 239000010959 steel Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 6
- 239000008397 galvanized steel Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000005282 brightening Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000004040 coloring Methods 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- -1 silver ions Chemical class 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910018605 Ni—Zn Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 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
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Description
（産業上の利用分野）
本発明は装飾が必要な部材に用いられる着色特
に黒色鋼板の製造方法に関するものである。
（従来の技術）
低コストで高性能の表面処理鋼板の開発は自動
車防錆鋼板、家庭用鋼板、家具および建材分野で
一貫して要求されつづけて来た。これらの要求水
準は年々低コスト化、高品質化に移行し、スチー
ルメーカーは新技術、新製品を開発し需要家の要
求に答えて来た。近年は、従来の表面処理鋼板を
加工した後前処理塗装されて来た製品に対してプ
レコートされた鋼板を導入することによつて、需
要家工程で行つていた前処理、塗装を省略し、低
コストで高品質の製品を得るプレコート鋼板化へ
の動きが活発である。これらの要求に答えるた
め、従来は塗料を塗装したプレコート鋼板が用い
られて来たが、徹底したコストダウン化、高級外
観、溶接性および取り扱い傷の問題から、無機系
の着色鋼板の要求が強くなつて来た。
色調としては黒色系統のニーズが強く、上述の
他指紋がつきに難いことや加工性、耐薬品性そし
て耐食性が要求される。
従来の着色処理法はステンレスや鋼板、銅が一
般的であるが、コストの点や、耐食性の観点から
亜鉛メツキ鋼板が本目的には合致しているので、
その黒色化に関する従来技術について以下述べ
る。
亜鉛メツキ又は亜鉛合金メツキ鋼板の黒色化法
として知られる公知の技術は、銀イオンを含むク
ロメート水溶液中で処理する黒色クロメートとし
て特開昭52−45544号公報記載の方法、あるいは
実務表面技術誌32巻第10号p541、表３、表５等
記載の技術がある。これらは酸化銀をクロメート
被膜と共に共析させて黒色面を得る方法である。
硬化物を形成させて黒色外観を得る方法として特
開昭52−65139号公報記載のものがある。又、特
開昭58−151490号公報および特開昭58−151491号
公報は陽極電解処理によつて黒色化する方法を開
示している。前者はNi2+、Co2+、Mo2+とZn2+の
合金メツキ浴中、後者はNi、Co、MoとZnの合
金メツキ鋼板を硫酸アンモニウム水溶液中で陽極
処理することによつてNi、Co、Moの酸化物を形
成させる方法である。又、特開昭60−121275号公
報は硝酸又は次亜塩素酸塩の水溶液でNi−Znの
合金メツキ鋼板を化学的に溶解して黒色外観を得
る方法を開示している。
又、特開昭60−200996号公報はZn2+とNi2+の
合金メツキ浴中で陰極電解によりNiを15％以上
含む合金亜鉛メツキ鋼板を得ることで黒色化する
方法を開示している。
（発明が解決しようとする問題点）
以上述べた従来の方法は必ずしも最良の方法と
は言えず、多くの問題点を抱えている。例えば銀
イオンによる方法はコストが高く、又高生産性に
難がある。又、陽極処理は素地のメツキの溶解が
大きく、素地のメツキが限定される上、一度析出
させたメツキを再溶解する無理がある。
又、特開昭60−200996号公報の方法は、得られ
る皮膜がNiとZnの黒色合金メツキ被膜であるた
め、黒色を得るために電流密度の制限や浴温、お
よび下地メツキが亜鉛又は亜鉛系合金メツキに限
定される等、生産する上で困難を伴う方法であ
る。
本発明はこれらの問題を解決したもので、高速
短時間処理が可能で、下地金属に依存しない着色
処理方法に基づく着色表面処理鋼板の製造方法を
提供するものである。
（問題点を解決するための手段）
本発明の製造方法は、Zn2+が20〜100ｇ／、
Men+が10〜50ｇ／で且つMen+／Zn2+の比が
0.1〜1.0であり、OXが１〜50ｇ／を主成分と
するPH＝１〜４の酸性水溶液中で鋼板またはメツ
キ鋼板を陰極として電流密度10〜100A／ｄm2で
20〜200クーロン／ｄm2電解処理し、水洗したの
ち、3μ以下のガードコートをコーテイングする
ことを特徴とする着色亜鉛複合メツキ鋼板の製造
方法である。Men+がNi2+、Co2+、Fe2+、
Fe3+Cr3+、Sn2+、Cu2+の１種以上、OXがNO3 -、
NO2 -、ClO4 -、ClO3 2-の１種であることは好ま
しい。また、酸性水溶液中に光沢剤を添加するこ
とも好ましい。
本発明は亜鉛と黒色の酸化物を金属表面に陰極
析出させる技術に基づいている。従来から亜鉛メ
ツキ等でメツキ結晶の粗いメツキ焼け等の現象で
黒色系統のメツキ不良が観察されていた。しか
し、これらの品質は文字通り悪く、又不均一であ
り、実用面での利用は皆無であつた。
本発明における最も重要な点は、酸化物が黒色
である金属イオンを含む合金メツキ浴に水溶性の
強酸化性のアニオンを導入し、着色被膜の形成条
件および品質を著るしく向上したことである。以
下本発明について詳述する。
（作用）
本発明の着色表面処理の組成およびその形成メ
カニズムについて述べる。
処理浴中には亜鉛イオン（Zn2+）、黒色化金属
イオン（Men+）および強酸化性イオン（OX）、
プロトン（H+）が存在する。
第１図に示した如く、陰極面ではZn2+の還元
により亜鉛の析出が生ずる。同時に着色化金属イ
オン（Men+）も還元されるが、メツキ浴中のOX
のため析出と同時に酸化され、酸化物を主体とす
るMeO（●印）が析出する。亜鉛も一部はZnOと
して析出するが、充分に低い還元電位にあるため
亜鉛として優先析出する。水素の発生は、水素過
電圧の高い亜鉛の析出により抑制される。
Men+はOXで酸化されて着色化するNi2+、
Co2+、Fe2+、Fe3+、Cr3+、Sn2+、Cu2+で、単独
もしくは複合することによつて着色することが出
来る。
OXは強酸化性のアニオンでNO3 -、NO2 -、
ClO4 -、ClO3 2-の１種を含む水溶液である。
本発明において、亜鉛は着色複合メツキ被膜の
展色剤的な役割を果たす。酸化物と亜鉛の混合比
が不適当だと、表層にパウダリングが生ずる。密
着性の良い着色被膜を得るのは適正なMen+／Zn
比との適度の酸化力、およびPHを選定することに
よつて達成できる。
又、メツキ浴中に光沢剤を加えると形成する複
合メツキ被膜が緻密になり、品質が向上する。
第２図は着色表面処理鋼板の構成図である。Ｓ
はベースの金属素地で、薄鋼板、ステンレス鋼
板、メツキ鋼板、例えば亜鉛および亜鉛合金メツ
キ鋼板、アルミおよびアルミ合金メツキ鋼板、ス
ズ、鉛メツキ鋼板である。Ｂは本発明によつて形
成される着色亜鉛複合メツキ層、Ｇはガードコー
トで、Gcはガードコートの内クロメート被膜を
示したものであり、Ｚはメツキ層である。
第２図ａは鋼板に直接着色した例を示す。同図
ｂはメツキ鋼板を着色した例、同図ｃはＢ上にク
ロメート処理を行い、ガードコートを被覆した例
を示す。
金属と着色化合物の複合被膜であり、着色の度
合によつて付着量が異る。着色外観を得るは少く
とも0.1ｇ／m2以上の付着量が必要である。黒色
外観では1.0ｇ／m2以上が望ましい。
余り複合メツキ被膜が厚すぎるとパウダリング
と称する表面粉化現象が生じるため、５ｇ／m2以
下が適当である。
本発明法による着色亜鉛複合メツキ鋼板は、着
色複合メツキ被膜上にガードコートを被覆する。
ガードコートは品質の向上が目的である。例えば
ガードコートを塗布することにより外観は均一性
が向上し、着色度も強くなる。光沢はガードコー
トの種類や厚みによつて半光沢から光沢までの外
観を有する鋼板が得られる。又、疵に対する抵抗
力が向上する。プレスや取扱い、当り傷に対して
特に有効である。耐食性は特に向上効果が大き
い。
本発明におけるガードコートは(1)化成処理被
膜、例えばクロメート被膜、リン酸塩被膜、キレ
ート被膜等の化学反応を伴つて形成する被膜、(2)
樹脂被膜、(3)無機ポリマー被膜、(4)樹脂と無機ポ
リマーの複合被膜、(5)油、油脂、ワツクス類であ
り、これらの単独もしくは複層化した被膜で構成
されている。
膜厚は外観および溶接性等に害がないように配
慮する必要があり、多くとも全厚みで3μ以下、
好ましくは1.5μ以下である。
樹脂（有機ポリマー）は、水溶性又は水分散性
溶剤溶性の有機高分子化合物を硬化剤と共にコー
テイングし、焼付等によつて硬化させた皮膜、あ
るいは紫外線硬化させた塗膜、あるいは無機有機
化合物を複合させた複合ポリマーを必要により硬
化剤と共にコーテイングし焼付等で硬化させた皮
膜である。複合させる化合物としては、クロム化
合物、シリカ、チタニア、アルミナ、ジルコニヤ
等の酸化物、マイカ、タルク、リン酸塩、ホウ酸
塩等の無機化合物脂肪酸石鹸類、カーボン、脂肪
酸エステル、プラスチツク粒子の有機化合物、シ
ランカツプリング剤、チタンカツプリング剤等の
有機金属化合物である。
又、無機ポリマーとしては、ケイ酸ナトリウ
ム、リチウムシリケートのケイ酸塩化合物および
ゾル、縮合リン酸ポリマー、重リン酸塩、ジルコ
ン酸ポリマー類である。
オイル及び油脂ワツクスは公知のもので良い。
又、本発明による着色亜鉛複合メツキ鋼板は着
色複合メツキ被膜およびガードコートの厚みが薄
いため、素地金属の表面状態、例えば光沢、粗度
を生かした外観および品質を得ることが出来る特
徴がある。
以下、本発明の着色亜鉛複合メツキ鋼板の製造
方法について述べる。
本発明に用いる処理浴成分について述べる。
亜鉛イオンは極めて重要な役割を果す。亜鉛イ
オンは陰極で亜鉛として析出し、水素の発生を抑
え防錆力を与えると共に、被膜のバインダー的役
割および電流効率を向上し、外観を均一化する。
添加量は、Zn2+として20〜100ｇ／、硫酸亜
鉛（ZnSo4、7H2O）として88〜440ｇ／、望ま
しくはZn2+30〜90ｇ／である。即ち、少なす
ぎると水素ガスの発生に支配され、高すぎると金
属亜鉛の析出が多くなり着色し難い。
次に、着色化金属イオンMen+について述べる。
本発明は可成りの金属イオンによつて黒色系統
の被膜が得られるが、その内、Ni2+、Co2+、
Fe2+、Fe3、Cr3+、Sn2+、Cu2+が黒色を得るのに
適している。濃度はMen+として1.0〜50ｇ／
で、Zn2+とのバランスがMen+／Zn2+比で0.1〜
1.0である。望ましい比は0.2〜0.5で、Zn2+が多い
方が良質の黒色被膜を得やすい。即ち、Men+／
Zn2+が低すぎると黒色化が不充分であり、高す
ぎるとパウダリングが発生する。
Zn2+、Men+の供給としては硫酸塩、塩化物、
リン酸塩、スルホン酸塩で、補給として炭酸塩、
酸化物、水酸化物、金属粉等が利用できる。
OXはNO3 -、NO2 -、ClO4 -、ClO3 2-の内から
選択するイオンで、可溶性の塩、酸として供給す
る。濃度はイオンとして１〜50ｇ／が適当であ
る。１ｇ／未満では充分な酸化物が形成しない
ため着色しない。又、50ｇ／超では全ての金属
を酸化するようになり、着色が難しく、又、パウ
ダリングが生じ易くなる。
黒色を得るのに好ましい濃度は５〜30ｇ／で
ある。
OXは陰極部で消耗するため補給する。
水溶液のPHは金属塩が沈澱しない４以下で、且
つ金属析出が生じ易い１〜４とする。
浴温は広範囲にわたり着色化可能であるが、好
ましくは30〜60℃である。
本発明法によつて得られる着色被膜は、Zn2+、
Men+、OX以外に光沢剤を加えた酸性水溶液を用
いることにより、品質特に光沢、パウダリング、
ガードコートとの密着性等が向上する。
光沢剤としては、水溶性の高分子化合物、例え
ばカオチン系の４級アンモニウム塩のポリアミン
系高分子、ポリアミンスルホン高分子化合物、お
よび非イオン系ポリアクリルアマイド化合物や、
これらとアニオン系との共重合体や、公知の光沢
剤として知られているアルデヒドやフエノール系
化合物、スルホン酸化合物が利用できる。
添加量は化合物の種類によつて異り、10〜
40000ppmの範囲で適宜加える。
以下、電解条件について述べる。
本発明は従来の方法に比べ着色化領域の広い条
件を選定できる極めて優れた方法である。電流密
度は10〜100A／ｄm2とする。10A／ｄm2未満で
は着色化が難しい。又100A／ｄm2超では水素ガ
スが発生し、出来た被膜が脱膜する危険度が高
い。通電量は20〜200クーロン／ｄm2とする。20
クーロン／ｄm2未満は着色が困難で、むらのある
外観になり易い。又、200クーロン／ｄm2超では、
脱膜や水素ガスによるピンホールのダメージが生
じ易くなる。
流速は静止浴でも高流速いずれでも良い。
被処理面は冷延鋼板、亜鉛合金メツキ鋼板、亜
鉛メツキ鋼板、光沢亜鉛メツキ鋼板、スズメツキ
鋼板等に試みた結果、全て着色し、黒色の場合、
冷延鋼板、亜鉛合金メツキ鋼板が黒さの点、傷付
き難くさの点で優れていた。
本発明の場合、必要により次の様な目的で別の
化合物を加えることができる。溶液の電導性を上
げるための各種支持塩、PH緩衝剤としてのホウ酸
塩やリン酸塩、フタル酸塩、密着加工性を向上さ
せるポリマー類、防錆性やガードコートとの接着
力を上げるリン酸塩やクロム酸塩、無機ゾル化合
物、カチオンポリマー、沈澱防止のためのキレー
ト剤、形成する亜鉛複合メツキ被膜の平滑性を与
える塩化物、フツ素化合物等である。
カードコートのコーテイング方法としては公知
のロールコート、ロール絞り法、スプレー、エア
ーナイフ絞り、浸漬ぬり、電解処理方法、静電塗
布法で塗布したのち、必要により加熱（熱風、赤
外線、燃焼炉、電熱）あるいは紫外線硬化等が採
用できる。
（実施例）
以下実施例を挙げる。
特に説明のない限り、Zn2+、Men+は硫酸塩か
ら建浴し、OX-はナトリウム塩を用いた。
電流密度はDkと示し、単位はＡ／ｄm2である。
通電量はＱと示し、単位はクーロン／ｄm2であ
る。着色亜鉛複合メツキの付着量はCWで示し、
重量法で測定し、ｇ／m2で示した。
Ｌ値は明度で市販の色差計で測定した。黒色度
との関連ではＬ値は25以下が必要である。
特に説明のない実施例については、次のような
ガードコートを行つた。
ガードコートの内、クロメートはシリカとクロ
ム酸からなる複合クロメートで、Crとして20
mg／m2付着させたもの、ポリマー被膜は市販の水
系のオレフインアクリル系とシリカゾルのクリヤ
ー塗膜を用いた。膜厚は約1μを狙い値としてロ
ールコート塗装し、熱風で板温100℃を狙つて焼
付けた。
品質の内、密着性は180度の曲げ加工後テーピ
ング剥離し、目視で、
○（剥離なし）
△（点状にテープ付着）
×（完全ハクリ）
で評価した。
又、耐食性はJISZ 2371規格の塩水噴霧試験の
連続法で試験し、面積比で５％錆発生するまでの
時間で示した。
実施例 １
冷延鋼板に公知の方法で硫酸浴から電気亜鉛メ
ツキを行つた後水洗し、ただちに第１表に示す着
色処理を行つたのちガードコートを塗装し、焼付
けた。電解処理は試料を陰極、鉛板を陽極として
通電した。
着色処理後水洗し、熱風乾燥後Ｌ値を色差計で
測定した。
(Industrial Application Field) The present invention relates to a method for manufacturing colored steel sheets, particularly black steel sheets, used for members that require decoration. (Prior Art) The development of low-cost, high-performance surface-treated steel sheets has been consistently required in the fields of automobile anticorrosive steel sheets, household steel sheets, furniture, and building materials. These requirements have shifted to lower costs and higher quality year by year, and steel manufacturers have developed new technologies and products to meet the demands of customers. In recent years, by introducing pre-coated steel sheets to products that were conventionally processed from surface-treated steel sheets and then pre-treated and painted, the pre-treatment and painting that were performed in the customer process can be omitted. There is a growing movement towards the use of pre-painted steel sheets to obtain high-quality products at low cost. In order to meet these demands, pre-painted steel sheets have traditionally been used, but due to issues such as thorough cost reduction, high-quality appearance, weldability, and handling scratches, there is a strong demand for inorganic colored steel sheets. I'm getting used to it. There is a strong need for a black color tone, and it is also required to be resistant to the aforementioned fingerprints, processability, chemical resistance, and corrosion resistance. Conventional coloring methods commonly use stainless steel, steel sheets, and copper, but galvanized steel sheets are suitable for this purpose from the viewpoint of cost and corrosion resistance.
The conventional technology related to the blackening will be described below. Known techniques for blackening zinc-plated or zinc-alloy plated steel sheets include the method described in Japanese Patent Application Laid-Open No. 52-45544, or the method described in Jitsugyo Surface Technology 32, in which black chromate is treated in an aqueous chromate solution containing silver ions. There are techniques described in Vol. 10, p. 541, Table 3, Table 5, etc. These methods involve eutectoiding silver oxide with a chromate film to obtain a black surface.
As a method of forming a cured product to obtain a black appearance, there is a method described in JP-A-52-65139. Further, Japanese Patent Application Laid-open No. 58-151490 and Japanese Patent Application Laid-Open No. 58-151491 disclose a method of blackening by anodic electrolytic treatment. The former is produced in an alloy plating bath of Ni 2+ , Co 2+ , Mo 2+ and Zn 2+ , and the latter is produced by anodizing a steel plate plated with an alloy of Ni, Co, Mo and Zn in an ammonium sulfate aqueous solution. This is a method of forming oxides of Co and Mo. Furthermore, Japanese Patent Application Laid-open No. 121275/1983 discloses a method of obtaining a black appearance by chemically dissolving a Ni-Zn alloy plated steel sheet in an aqueous solution of nitric acid or hypochlorite. Furthermore, JP-A-60-200996 discloses a method for blackening an alloy galvanized steel sheet containing 15% or more of Ni by cathodic electrolysis in an alloy plating bath of Zn 2+ and Ni 2+ . . (Problems to be Solved by the Invention) The conventional methods described above are not necessarily the best methods and have many problems. For example, methods using silver ions are expensive and have difficulty in achieving high productivity. In addition, anodizing significantly dissolves the plating on the substrate, which limits the plating on the substrate, and it is difficult to re-dissolve the plating once deposited. In addition, in the method of JP-A-60-200996, the resulting film is a black alloy plating film of Ni and Zn, so in order to obtain a black color, the current density must be limited, the bath temperature, and the base plating must be zinc or zinc. This method is difficult to produce as it is limited to plating based on alloys. The present invention solves these problems and provides a method for manufacturing a colored surface-treated steel sheet based on a coloring method that is capable of high-speed, short-time processing and does not depend on the underlying metal. (Means for solving the problems) The production method of the present invention includes Zn 2+ of 20 to 100 g/,
Me n+ is 10 to 50 g/and the ratio of Me n+ /Zn 2+ is
0.1 to 1.0 and a current density of 10 to 100 A/dm 2 using a steel plate or plated steel plate as a cathode in an acidic aqueous solution with PH = 1 to 4 containing OX of 1 to 50 g/ as the main component.
This is a method for producing a colored zinc composite galvanized steel sheet, which is characterized in that the steel sheet is electrolytically treated at 20 to 200 coulombs/ dm2 , washed with water, and then coated with a guard coat of 3μ or less. Me n+ is Ni 2+ , Co 2+ , Fe 2+ ,
One or more of Fe 3+ Cr 3+ , Sn 2+ , Cu 2+ , OX is NO 3 - ,
It is preferable that it is one of NO 2 - , ClO 4 - , and ClO 3 2- . It is also preferable to add a brightener to the acidic aqueous solution. The invention is based on the cathodic deposition of zinc and black oxide onto metal surfaces. In the past, defective plating of black color has been observed due to phenomena such as coarse plating crystals and burnt plating in zinc plating. However, the quality of these materials was literally poor and non-uniform, so they were of no practical use. The most important point of the present invention is that water-soluble strongly oxidizing anions are introduced into the alloy plating bath containing metal ions whose oxides are black, thereby significantly improving the formation conditions and quality of the colored film. be. The present invention will be explained in detail below. (Function) The composition of the colored surface treatment of the present invention and its formation mechanism will be described. The treatment bath contains zinc ions (Zn 2+ ), blackening metal ions (Me n+ ), and strong oxidizing ions (OX).
Protons (H + ) are present. As shown in FIG. 1, zinc is deposited on the cathode surface due to the reduction of Zn 2+ . At the same time, colored metal ions (Me n+ ) are also reduced, but OX in the plating bath
Therefore, it is oxidized at the same time as it is precipitated, and MeO (marked with ●), which is mainly an oxide, is precipitated. A portion of zinc also precipitates as ZnO, but because the reduction potential is sufficiently low, it preferentially precipitates as zinc. Hydrogen evolution is suppressed by zinc deposition with high hydrogen overpotential. Me n+ is oxidized by OX and becomes colored Ni 2+ ,
It can be colored with Co 2+ , Fe 2+ , Fe 3+ , Cr 3+ , Sn 2+ , and Cu 2+ alone or in combination. OX is a strong oxidizing anion that produces NO 3 - , NO 2 - ,
It is an aqueous solution containing one of ClO 4 - and ClO 3 2- . In the present invention, zinc plays the role of a color vehicle for the colored composite plating film. If the mixing ratio of oxide and zinc is inappropriate, powdering will occur on the surface layer. Proper Me n+ /Zn to obtain a colored film with good adhesion
This can be achieved by selecting an appropriate oxidizing power and pH ratio. Furthermore, when a brightening agent is added to the plating bath, the composite plating film formed becomes denser and the quality is improved. FIG. 2 is a configuration diagram of a colored surface-treated steel sheet. S
is the base metal substrate, such as thin steel plate, stainless steel plate, plated steel plate, such as zinc and zinc alloy plated steel plate, aluminum and aluminum alloy plated steel plate, tin, and lead plated steel plate. B is a colored zinc composite plating layer formed according to the present invention, G is a guard coat, Gc is a chromate coating within the guard coat, and Z is a plating layer. Figure 2a shows an example in which a steel plate is directly colored. Figure b shows an example in which a plated steel plate is colored, and figure c shows an example in which B is subjected to chromate treatment and covered with a guard coat. It is a composite film of metal and colored compound, and the amount of adhesion varies depending on the degree of coloring. To obtain a colored appearance, a coating amount of at least 0.1 g/m 2 or more is required. For black appearance, 1.0 g/m 2 or more is desirable. If the composite plating film is too thick, a surface pulverization phenomenon called powdering will occur, so a thickness of 5 g/m 2 or less is appropriate. In the colored zinc composite plating steel sheet produced by the method of the present invention, a guard coat is coated on the colored composite plating film.
The purpose of the guard coat is to improve quality. For example, by applying a guard coat, the uniformity of the appearance improves and the degree of coloring becomes stronger. Depending on the type and thickness of the guard coat, a steel plate with an appearance ranging from semi-gloss to gloss can be obtained. Also, resistance to scratches is improved. Particularly effective against press, handling, and contact scratches. The effect of improving corrosion resistance is particularly large. The guard coat in the present invention includes (1) a chemical conversion coating, such as a chromate coating, a phosphate coating, a chelate coating, etc., which is formed through a chemical reaction;
These are resin coatings, (3) inorganic polymer coatings, (4) composite coatings of resin and inorganic polymers, and (5) oils, oils, and waxes, and these coatings may be used singly or in multiple layers. The film thickness must be considered so as not to harm the appearance and weldability, and the total thickness should be 3μ or less at most.
Preferably it is 1.5μ or less. Resin (organic polymer) is a film made by coating a water-soluble or water-dispersible solvent-soluble organic polymer compound with a curing agent and hardening it by baking, etc., a coating film cured by ultraviolet rays, or an inorganic organic compound. It is a film made by coating a composite polymer with a hardening agent if necessary and hardening it by baking or the like. Compounds include chromium compounds, oxides such as silica, titania, alumina, and zirconia, inorganic compounds such as mica, talc, phosphates, and borates, fatty acid soaps, carbon, fatty acid esters, and organic compounds such as plastic particles. , silane coupling agents, titanium coupling agents, and other organometallic compounds. Examples of inorganic polymers include silicate compounds and sols of sodium silicate and lithium silicate, condensed phosphoric acid polymers, biphosphates, and zirconic acid polymers. Known oils and fat waxes may be used. Furthermore, the colored zinc composite plated steel sheet according to the present invention has a thin colored composite plating film and guard coat, so that it is possible to obtain an appearance and quality that takes advantage of the surface condition of the base metal, such as gloss and roughness. The method for manufacturing the colored zinc composite plated steel sheet of the present invention will be described below. The processing bath components used in the present invention will be described. Zinc ions play a vital role. Zinc ions precipitate as zinc at the cathode, suppressing hydrogen generation and providing anti-rust properties, as well as acting as a binder for the coating, improving current efficiency, and making the appearance uniform. The amount added is 20 to 100 g/as Zn 2+ and 88 to 440 g/as zinc sulfate (ZnSo 4 , 7H 2 O), preferably 30 to 90 g/Zn 2+ . That is, if it is too low, it will be dominated by the generation of hydrogen gas, and if it is too high, metallic zinc will be deposited in large quantities, making it difficult to color. Next, the colored metal ion Men + will be described. In the present invention, a blackish coating can be obtained by using a considerable amount of metal ions, among which Ni 2+ , Co 2+ ,
Fe 2+ , Fe 3 , Cr 3+ , Sn 2+ and Cu 2+ are suitable for obtaining black color. Concentration is 1.0-50g/ as Me n+
So, the balance with Zn 2+ is Me n+ /Zn 2+ ratio of 0.1~
It is 1.0. The desirable ratio is 0.2 to 0.5; the more Zn 2+ there is, the easier it is to obtain a high-quality black film. That is, Men + /
If Zn 2+ is too low, blackening is insufficient, and if it is too high, powdering occurs. Sulfate , chloride ,
With phosphates, sulfonates, carbonates as supplements,
Oxides, hydroxides, metal powders, etc. can be used. OX is an ion selected from NO 3 - , NO 2 - , ClO 4 - , and ClO 3 2- , and is supplied as a soluble salt or acid. The appropriate concentration is 1 to 50 g/ion. If it is less than 1 g/g, sufficient oxide will not be formed and no color will be produced. Moreover, if it exceeds 50 g/g, all the metals will be oxidized, making coloring difficult and powdering likely to occur. Preferred concentrations are between 5 and 30 g/g to obtain a black color. OX is consumed in the cathode section, so it must be replenished. The pH of the aqueous solution is 4 or less, at which metal salts do not precipitate, and 1 to 4, at which metal precipitation is likely to occur. The bath temperature can be colored over a wide range, but is preferably 30 to 60°C. The colored film obtained by the method of the present invention contains Zn 2+ ,
By using an acidic aqueous solution containing a brightening agent in addition to Men + and OX, quality, especially gloss, powdering, and
Improves adhesion with the guard coat. As the brightening agent, water-soluble polymer compounds such as polyamine polymers of cationic quaternary ammonium salts, polyamine sulfone polymer compounds, and nonionic polyacrylamide compounds,
Copolymers of these and anionic compounds, aldehydes, phenolic compounds, and sulfonic acid compounds known as known brightening agents can be used. The amount added varies depending on the type of compound, from 10 to
Add as appropriate within the range of 40,000ppm. The electrolysis conditions will be described below. The present invention is an extremely superior method that allows selection of a wider range of conditions for coloring than conventional methods. The current density is 10 to 100 A/dm 2 . Coloring is difficult at less than 10 A/dm 2 . Moreover, if it exceeds 100 A/dm 2 , hydrogen gas will be generated and there is a high risk that the formed film will come off. The amount of current applied is 20 to 200 coulombs/ dm2 . 20
If it is less than coulomb/dm 2 , coloring is difficult and tends to give an uneven appearance. Also, at over 200 coulombs/dm 2 ,
Pinhole damage due to film removal and hydrogen gas is more likely to occur. The flow rate may be either a static bath or a high flow rate. As a result of attempts to treat cold rolled steel plates, zinc alloy plated steel plates, galvanized steel plates, bright galvanized steel plates, tin plated steel plates, etc., all surfaces were colored, and in the case of black,
Cold-rolled steel sheets and zinc alloy plated steel sheets were superior in terms of blackness and scratch resistance. In the case of the present invention, other compounds may be added if necessary for the following purposes. Various supporting salts to increase the conductivity of solutions, borates, phosphates, and phthalates as PH buffers, polymers to improve adhesion processability, and rust prevention and to increase adhesive strength with guard coats. These include phosphates, chromates, inorganic sol compounds, cationic polymers, chelating agents to prevent precipitation, chlorides and fluorine compounds that provide smoothness to the zinc composite plating film formed. Coating methods for card coating include roll coating, roll drawing, spraying, air knife drawing, dipping, electrolytic treatment, and electrostatic coating, followed by heating (hot air, infrared rays, combustion furnace, electric heating) if necessary. ) or ultraviolet curing can be used. (Example) Examples will be given below. Unless otherwise specified, Zn 2+ and Men + were prepared from sulfate, and OX - was prepared using sodium salt. The current density is denoted as Dk, and the unit is A/dm 2 .
The amount of current is indicated as Q, and the unit is coulomb/dm 2 . The coating weight of colored zinc composite plating is shown in CW,
It was determined gravimetrically and expressed in g/m 2 . The L value was measured by lightness using a commercially available color difference meter. In relation to blackness, the L value must be 25 or less. For Examples not specifically described, the following guard coating was applied. Chromate in Guard Coat is a composite chromate consisting of silica and chromic acid, and has a concentration of 20% as Cr.
mg/m 2 was applied, and the polymer film used was a commercially available water-based olefin acrylic system and silica sol clear coating. Roll coating was applied with a film thickness of approximately 1μ as the target value, and baking was performed using hot air to achieve a board temperature of 100°C. Among quality factors, adhesion was evaluated by peeling off the tape after 180 degree bending and visually evaluating it as ○ (no peeling), △ (tape attached in dots) × (complete peeling). Corrosion resistance was tested using a continuous salt spray test according to JISZ 2371 standard, and was expressed as the time required for 5% rust to occur in terms of area ratio. Example 1 A cold-rolled steel sheet was electrogalvanized in a sulfuric acid bath using a known method, washed with water, immediately subjected to the coloring treatment shown in Table 1, and then coated with a guard coat and baked. In the electrolytic treatment, electricity was applied using the sample as a cathode and the lead plate as an anode. After coloring, the sample was washed with water, dried with hot air, and the L value was measured using a color difference meter.
【表】【table】
【表】
No.１〜５はOXとして硝酸ナトリウムを用いて
Zn2+とNi2+の比を変化させたときのデータで、
Ni2+／Zn2+＝0.2〜1.0の範囲で低いＬ値の外観が
得られている。
No.６〜９はZn2+とFe2+の浴を用いて電流密度
を10〜100A／ｄm2に変化させた例で、10A／ｄ
m2ではややＬ値が高くなる傾向にあり、100A／
ｄm2では点状の剥離が発生し始める。No.10はPHを
1.2にした例であり、低いPHでも低Ｌ値が得られ
た。No.11はOX-を含まない例を示したもので、
Ｌ値が高いものしか得られない。
No.12、13はMen+として複合浴を用いた例で、
低いＬ値が得られている。
No.14〜18はZn2+濃度とFe／Zn2+比を変化させ
たデータである。Zn2+が低すぎると白つぽくな
る。又比が３に近くになるとＬ値が高くなる。
No.19はMen+としてFe2+およびFe3+の複合添加
浴でFe3+の影響は少い。
No.20〜22はOXとしてNO2 -、ClO4 -、ClO3 2-、
Fe3+を用いた例で、酸化作用の弱いNO2 -、
ClO3 2-はClO4、NO3 -に比べるとややＬ値が高い
傾向にある。
No.23〜24はMen+としてNi2+、Co2+の複合添加
で且つPHを変化させた場合の例である。PH＝１付
近ではＬ値が高くなり、エツチングが生じ、むら
が出ている。
No.25〜30はOX-としてNO3 -の濃度を変化させ
た例で、NO3 -は50、100ｇ／の浴ではＬ値が
高く、限界値である。NO3 -が５、10、20ｇ／
では充分なＬ値が得られている。
No.31〜33はクーロン量を変化させた例で、25ク
ーロンではややＬ値が高く、200クーロンではパ
ウダリングが生じている。
実施例 ２
硫酸亜鉛400ｇ／（Zn2+92）、硫酸ニツケル
100ｇ／（Ni2+20）、Ni2+／Zn2+比0.22、
NaNO320ｇ／、PH＝1.5、浴温50℃の水溶液中
で鉛板を対極として第２表に示す各種鋼板および
メツキ鋼板を陰極として電解処理（50A／ｄm2、
50クーロン／ｄm2）したのち、実施例１と同様の
ガードコートを行つた。[Table] Nos. 1 to 5 use sodium nitrate as OX.
Data when changing the ratio of Zn 2+ and Ni 2+ ,
An appearance with a low L value is obtained in the range of Ni 2+ /Zn 2+ =0.2 to 1.0. Nos. 6 to 9 are examples in which the current density was changed from 10 to 100 A/dm 2 using a bath of Zn 2+ and Fe 2+ .
m 2 tends to have a slightly higher L value, 100A/
At dm 2 , point-like peeling begins to occur. No.10 has PH
This is an example where the pH was set to 1.2, and a low L value was obtained even at a low pH. No.11 shows an example that does not contain OX - .
Only products with high L values can be obtained. Nos. 12 and 13 are examples of using a composite bath as Me n+ .
A low L value is obtained. Nos. 14 to 18 are data obtained by changing the Zn 2+ concentration and Fe/Zn 2+ ratio. If Zn 2+ is too low, it will look whitish. Also, as the ratio approaches 3, the L value increases. No. 19 is a mixed bath of Fe 2+ and Fe 3+ as Me n+, and the influence of Fe 3+ is small. No. 20 to 22 are NO 2 - , ClO 4 - , ClO 3 2- ,
In the example using Fe 3+ , NO 2 - , which has a weak oxidizing effect,
ClO 3 2- tends to have a slightly higher L value than ClO 4 and NO 3 - . Nos. 23 to 24 are examples in which Ni 2+ and Co 2+ are added in combination as Men + and the PH is changed. Around PH=1, the L value becomes high, etching occurs, and unevenness appears. Nos. 25 to 30 are examples in which the concentration of NO 3 - was changed as OX - , and NO 3 - has a high L value in a bath of 50 or 100 g/, which is the limit value. NO 3 - is 5, 10, 20g/
A sufficient L value is obtained. Nos. 31 to 33 are examples in which the amount of coulombs was changed; at 25 coulombs, the L value was slightly high, and at 200 coulombs, powdering occurred. Example 2 Zinc sulfate 400g/(Zn 2+ 92), nickel sulfate
100g/(Ni 2+ 20), Ni 2+ /Zn 2+ ratio 0.22,
Electrolytic treatment (50 A /dm 2 ,
50 coulombs/dm 2 ), and then a guard coat similar to that in Example 1 was applied.
【表】
本処理方法は被処理金属に依存し難く、鋼板お
よびメツキ鋼板を着色化できた。
実施例 ３
実施例２で用いた酸性水溶液に市販のポリアミ
ンスルホン高分子を8000ppm加えたＡ液、ポリア
クリルアミドを20ppm加えたＢ液を用いて実施例
２と同様の処理を12％Ni−Zn電気メツキ鋼板に
行つた。
Ｌ値がＡ＝11、Ｂ＝12で半光沢の加工性に優れ
た黒色鋼板を得た。
（発明の効果）
本発明による着色亜鉛複合メツキ鋼板は品質的
に外観、加工性、耐食性に優れ、疵に対しても強
い抵抗を有する新しい鋼板として従来の塗装鋼板
分野に使用でき、製品の高級化、低コストに貢献
する。
又、製造的に非常に広範囲な処理条件が適用で
き、高速短時間処理が可能なため、従来の電気メ
ツキライン内での処理が可能であり、低いコスト
で製造できる。
特に本発明は着色化において素地金属に依存せ
ず、通電する表面には容易に着色できる点で従来
の合金メツキあるいは合金を溶解させる方法に比
し有利である。[Table] This treatment method does not depend on the metal to be treated, and was able to color steel sheets and plated steel sheets. Example 3 The same treatment as in Example 2 was carried out using 12% Ni-Zn electric I went to Metsuki Steel Sheet. A semi-gloss black steel plate with L values of A=11 and B=12 and excellent workability was obtained. (Effect of the invention) The colored zinc composite plated steel sheet according to the present invention has excellent appearance, workability, and corrosion resistance, and can be used as a new steel sheet with strong resistance to scratches in the field of conventional coated steel sheets, and can be used as a high-quality product. This contributes to lower costs. In addition, since a very wide range of processing conditions can be applied in terms of manufacturing, and high-speed, short-time processing is possible, processing can be performed within a conventional electroplating line, and manufacturing can be performed at low cost. In particular, the present invention is advantageous over conventional alloy plating or alloy melting methods in that it does not depend on the base metal for coloring and can easily color the surface to which electricity is applied.
第１図は本発明の着色メカニズムとその皮膜の
構成を示した図であり、第２図ａ，ｂ，ｃは本発
明法による着色亜鉛複合メツキ鋼板の構成を示し
た図である。
FIG. 1 is a diagram showing the coloring mechanism of the present invention and the structure of its coating, and FIGS. 2a, b, and c are diagrams showing the structure of a colored zinc composite plated steel sheet by the method of the present invention.
Claims (1)
属イオンが10〜50ｇ／で且つMen+／Zn2+の比
が0.1〜1.0であり、OXで示す強酸化性のイオン
が１〜50ｇ／を主成分とするPH＝１〜４の酸性
水溶液中で鋼板またはメツキ鋼板を陰極として電
流密度10〜100A／ｄm2で20〜200クーロン／ｄm2
電解処理し、水洗したのち、3μ以下のガードコ
ートをコーテイングすることを特徴とする着色亜
鉛複合メツキ鋼板の製造方法。 ２ Men+がNi2+、Co2+、Fe2+、Cr2+、Fe3+、
Sn2+、Cu3+の１種以上、OXがNO3 -、NO2 -、
ClO4 -、ClO3 2-の１種である特許請求の範囲第１
項記載の方法。 ３ 酸性水溶液中に光沢剤を添加する特許請求の
範囲第１項記載の方法。[Claims] 1 Zn 2+ is 20 to 100 g/, colored metal ions indicated by Me n+ are 10 to 50 g/, and the ratio of Me n+ /Zn 2+ is 0.1 to 1.0, and the intensity indicated by OX is 0.1 to 1.0. In an acidic aqueous solution containing 1 to 50 g of oxidizing ions as a main component and having a pH of 1 to 4, a current density of 10 to 100 A/dm 2 is applied at a current density of 20 to 200 coulombs/dm 2 using a steel plate or a galvanized steel plate as a cathode.
A method for producing a colored zinc composite plated steel sheet, which comprises electrolytically treating it, washing it with water, and then coating it with a guard coat of 3μ or less. 2 Me n+ is Ni 2+ , Co 2+ , Fe 2+ , Cr 2+ , Fe 3+ ,
One or more of Sn 2+ , Cu 3+ , OX is NO 3 - , NO 2 - ,
Claim 1, which is one of ClO 4 - and ClO 3 2-
The method described in section. 3. The method according to claim 1, wherein a brightening agent is added to the acidic aqueous solution.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19261386A JPS6350499A (en) | 1986-08-18 | 1986-08-18 | Colored zinc composite plated steel sheet and its production |
| US07/084,727 US4861441A (en) | 1986-08-18 | 1987-08-13 | Method of making a black surface treated steel sheet |
| EP87111905A EP0259657B1 (en) | 1986-08-18 | 1987-08-17 | Black surface treated steel sheet and method for its production |
| ES87111905T ES2053484T3 (en) | 1986-08-18 | 1987-08-17 | STEEL PLATE TREATED WITH BLACK SURFACE AND METHOD FOR ITS PRODUCTION. |
| DE8787111905T DE3784416T2 (en) | 1986-08-18 | 1987-08-17 | SURFACE TREATED BLACK STEEL SHEET AND METHOD FOR PRODUCING THE SAME. |
| US07/350,436 US5011744A (en) | 1986-08-18 | 1989-05-11 | Black surface treated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19261386A JPS6350499A (en) | 1986-08-18 | 1986-08-18 | Colored zinc composite plated steel sheet and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6350499A JPS6350499A (en) | 1988-03-03 |
| JPH0340116B2 true JPH0340116B2 (en) | 1991-06-17 |
Family
ID=16294170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19261386A Granted JPS6350499A (en) | 1986-08-18 | 1986-08-18 | Colored zinc composite plated steel sheet and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6350499A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0247293A (en) * | 1988-08-09 | 1990-02-16 | Nippon Steel Corp | Production of plated steel sheet having superior spot weldability |
| JPH0637711B2 (en) * | 1989-06-22 | 1994-05-18 | 新日本製鐵株式会社 | Method for producing black surface-treated steel sheet |
| JPH09137290A (en) * | 1995-11-13 | 1997-05-27 | Sumitomo Metal Ind Ltd | Black zinc electroplated steel sheet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200996A (en) * | 1984-03-23 | 1985-10-11 | Sumitomo Metal Ind Ltd | Blackened rustproof steel sheet and its manufacture |
-
1986
- 1986-08-18 JP JP19261386A patent/JPS6350499A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200996A (en) * | 1984-03-23 | 1985-10-11 | Sumitomo Metal Ind Ltd | Blackened rustproof steel sheet and its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6350499A (en) | 1988-03-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0259657B1 (en) | Black surface treated steel sheet and method for its production | |
| JPH0324295A (en) | Production of black surface-treated steel sheet | |
| JPH0352557B2 (en) | ||
| JPH0340117B2 (en) | ||
| JPH0340116B2 (en) | ||
| JPH0679842B2 (en) | Black surface treated steel plate | |
| KR100614025B1 (en) | Resin coated steel sheet, cartridge cap and cartridge barrel using it | |
| JPH0216395B2 (en) | ||
| JPS63195296A (en) | Production of colored surface-treated steel sheet | |
| JPH0217633B2 (en) | ||
| JPH0369993B2 (en) | ||
| JP2816559B2 (en) | Manufacturing method of black galvanized steel sheet | |
| JPH0359996B2 (en) | ||
| JPH0232360B2 (en) | CHAKUSHOKUAENMETSUKIKOHANNOSEIZOHOHO | |
| JPS62180081A (en) | Colored galvanized steel sheet | |
| JPH01108396A (en) | Production of galvannealed steel sheet for coating by cationic electrodeposition | |
| JPH025839B2 (en) | ||
| JP2701145B2 (en) | Chromate conversion treatment method for steel plate | |
| KR100544646B1 (en) | Surface Treated Steel Sheet Having Excellent Corrosion Resistance And Manufacturing Method Thereof | |
| Samai | METALLIC COATINGS | |
| JPS62270799A (en) | Colored surface-treated steel sheet and its production | |
| JP3241170B2 (en) | Pretreatment method for cationic electrodeposition coating of aluminum-based metal materials | |
| JPH0456798A (en) | Production of chromated galvanized steel sheet excellent in resistance to corrosion and fingerprinting, coating suitability and surface color tone | |
| JPH0430476B2 (en) | ||
| JPH0565700A (en) | Resin coated zn-ni-cr-al2o3 type electroplated steel sheet and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |