JPH052744B2 - - Google Patents
Info
- Publication number
- JPH052744B2 JPH052744B2 JP59252355A JP25235584A JPH052744B2 JP H052744 B2 JPH052744 B2 JP H052744B2 JP 59252355 A JP59252355 A JP 59252355A JP 25235584 A JP25235584 A JP 25235584A JP H052744 B2 JPH052744 B2 JP H052744B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- less
- acid
- layer
- water
- 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 - Fee Related
Links
- 238000007747 plating Methods 0.000 claims description 72
- 239000011651 chromium Substances 0.000 claims description 69
- 229910000831 Steel Inorganic materials 0.000 claims description 24
- 239000010959 steel Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 9
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 10
- 238000002845 discoloration Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 but as is well known Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002355 dual-layer Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 150000004782 1-naphthols Chemical class 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
＜産業上の利用分野＞
本発明は、鋼板表面にCr、Snを順次積層する
２層めつき鋼板の製造方法に関するもので、特
に、Crめつき上のSnめつき量が、1.0ｇ／m2以下
であるSn／Cr2層めつき鋼板の製造方法に関する
ものである。
＜従来技術とその問題点＞
電気めつき法によりめつきされた金属Crの上
に電気Snめつきを施す場合、金属Cr表面にはCr
水和酸化物が存在するので、通常の電気Snめつ
き方法では満足なSnめつきを施すことができな
い。すなわち、通常工業的に行われている電気ク
ロムめつきは、Cr6+イオンを電気化学的に金属
Crまで還元するのであるが、周知の如く、Cr6+
イオンは３価Crの水和酸化物を経由して金属Cr
まで還元されるので、めつき表面には常にCr水
和酸化物が存在しており、このCr水和酸化物が
Snめつきを妨げるのである。金属Cr表面にCr水
和酸化物が存在している状態で電気Snめつきを
施しても、密着力の乏しいめつき層しか得られな
い。
したがつて、電気Snめつきを施すためには、
電気Crめつき表面のCr水和酸化物を除去しなけ
ればならない。
このCr水和酸化物を除去する方法としては、
熱アルカリ水溶液で溶解させる方法や、NaOH
水溶液、りん酸緩衝溶液、硼酸緩衝溶液等の水溶
液中で陽極電解により、溶解させる方法が知られ
ている。
熱アルカリ水溶液で溶解させる方法では、アル
カリに不溶なCr酸化物が残存して満足なSnめつ
きを施すことができない。また陽極電解処理で
は、金属Crも溶解し、金属Crが溶解消失するま
でCr水和酸化物が残存するので、Sn／Cr2層めつ
き鋼板の製造法に用いることはできない。
その他、特殊なSnめつき前処理として、先行
技術特公昭33−1455号「クロム及クロム合金表面
上への各種金属の鍍金法」があるが、開示されて
いるところの表面活性化処理を行つても、実用上
満足できる密着性を有するSnめつきを得ること
はできない。
さらに、先行技術特公昭48−35136号「クロム
−錫二層メツキ方法」があるが、開示されている
ところのCrめつき液浸漬処理によつても、Crめ
つき表面のCr水和酸化物は完全には除去されず、
十分なめつき密着力は得られない。また、非常に
高い電流密度のストライク処理を行うので設備上
実施が困難である等の問題がある。
＜発明の目的＞
本発明の目的は、上記従来の欠点を解消し、め
つき密着性に優れ、光沢の良い、耐変色性を有す
る、簡便なSn／Cr2層めつき鋼板の製造方法を提
供することにある。
本発明の第１の態様によれば、鋼板表面に電気
Crめつきを施した後、水洗し、Snイオン1.5〜10
ｇ／を含みPHが0.5未満０以上である強酸性Sn
めつき浴を用いて20〜50A／ｄm2で１ｇ／m2以下
のSnめつきを行い、水洗した後、10〜50ｇ／
のCrO3と硫酸、硫酸塩、フツ酸、フツ化物の１
種または２種以上を含む浴を用い電流密度10A／
ｄm2以上で換算で５〜30mg／m2の金属CrとCr水
和酸化物から成るクロメート被膜層を形成させる
ことを特徴とするSn／Cr2層めつき鋼板の製造方
法が提供される。
本発明の第２態様によれば、鋼板表面に電気
Crめつきを施した後、水洗し、Snイオン1.5〜10
ｇ／とオキシエチレン鎖を有する界面活性剤を
0.1〜10ｇ／を含みPHが0.5未満０以上である強
酸性Snめつき浴を用いて20〜50A／ｄm2で１ｇ／
m2以下のSnめつきを行い、水洗した後、10〜50
ｇ／のCrO3と硫酸、硫酸塩、フツ酸、フツ化
物の１種または２種以上を含む浴を用い電流密度
10A／ｄm2以上でCr換算で５〜30mg／m2の金属
CrとCr水和酸化物から成るクロメート被膜層を
形成させることを特徴とするSn／Cr2層めつき鋼
板の製造方法が提供される。
＜発明の具体的構成＞
以下、本発明を更に詳細に説明する。
本発明では、まず鋼板表面を常法により脱脂、
酸洗を行つた後、公知のCrめつき浴組成、めつ
き条件で電気Crめつきを行う。続いて十分な水
洗洗滌を行い、引き続いて、Snイオン1.5〜10
ｇ／を含みPHが0.5未満０以上である強酸酸性
浴中で20〜50A／ｄm2陰極電解を行い、Snめつき
を施す。
本発明におけるSnめつき浴におけるSnイオン
は、硫酸錫、塩化錫、ホウフツ化錫、ピロリン酸
錫、フツ化錫、およびその他の錫化合物を用いて
供給すれば良く、酸としては硫酸、塩酸、フツ
酸、ホウフツ酸等の無機酸、あるいはフエノール
スルホン酸、クレーゾールスルホン酸等の有機酸
を、それぞれ単独あるいは混合して用いれば良
い。
本発明のSnめつき法では、Snめつきと同時に
多量の活性なH2ガスが発生する。この多量の活
性なH2ガスにより、従来の方法では完全に除去
し得なかつた電気Crめつき表面上のCr水和酸化
物が完全に除去され、同時にSnが電着されるこ
とにより、密着性の優れたCrめつき上のSnめつ
きが達成されるのである。
Snめつき時にかなりのH2ガス発生を伴う条件
でめつきを行うと、H2ガスにより鋼板表面が活
性化されて、緻密なSnめつき層が得られること
が知られている。すなわち、特公昭45−19362号
「電気錫メツキ方法」、特公昭46−25603号「酸性
電気錫前メツキ法」に開示されているところで
は、電気Snめつき鋼板（通称ブリキと称される）
の耐食性を向上させる前処理として、H2ガスを
かなり発生する低Snイオン濃度浴を使うことが
示されており、また、特開昭55−73887号「酸性
錫めつき浴」に開示されているところでは、公知
の硫酸錫浴、フエノールスルホン酸錫浴に、硫酸
塩を添加して、H2ガスを発生させながら極薄Sn
めつきを行うことが示されている。
しかし、これらは、いずれも鋼板上に行うSn
めつきの改良に関する方法であり、めつきを阻害
するCr水和酸化物が存在するCrめつき上へのSn
めつきを対象としておらず、上記方法ではCrめ
つき上へ満足なSnめつきを施すことはできない。
これに対し本発明の製造方法は、従来困難であつ
たCrめつき上へのSnめつき法を提供するもので
ある。
本発明者らは既に、特願昭59−117704号「溶接
性に優れた表面処理鋼板及びその製造方法」にお
いて示したように、電気Crめつき後、塩酸、硫
酸、シユウ酸酢酸を１種または２種以上含有する
水溶液中で陰極電解することにより、効率良く電
気Crめつき表面の水和酸化物を除去できること
を知見している。また、該水溶液中に錫イオンを
含有させることにより、クロム水和酸化物を除去
すると同時にSnめつきが施せることを知見して
いる。本発明者らは、このSnイオンを含有する
酸溶液についてさらに検討を進めた結果、電気
Crめつき上に電気Snめつきを施すのに適正なSn
イオン濃度と水素イオン濃度（PH）を新規に見出
し、本発明に至つたものである。
本発明におけるめつき浴中のSnイオン濃度は
1.5〜10ｇ／、より好ましくは1.5〜５ｇ／で
ある。Snイオン濃度が1.5ｇ／未満ではSnが金
属Cr上に析出せず、10ｇ／を越えると粉末状、
あるいは樹枝状の析出となり、外観が極めて悪く
なり実用的でない。
本発明におけるSnめつき浴中の水素イオン濃
度は、PHで0.5未満０以上である。水素イオン濃
度がPHで0.5以上では、電気Crめつき表面のCr水
和酸化物を除去するのに必要な活性なH2ガスの
発生が不十分であり、密着力の不十分なSnめつ
きしか得られない。またPHが０未満では、活性な
H2ガスの発生は十分であるが、液の腐食性が強
くなり、めつき装置類に過剰な耐酸処置を講じね
ばならず、不経済である。めつき電流密度は20〜
50A／ｄm2が好ましい。20A／ｄm2未満では活性
なH2ガスの発生効率が悪くSnめつきに長時間を
要するので好ましくない。50A／ｄm2超では電源
装置が高価なものになるばかりでなくめつき液が
ジユール熱で発熱するので好ましくない。めつき
温度は30〜50℃が好ましい範囲である。H2ガス
を多量に発生させる本Snめつき法では、Snめつ
き量が１ｇ／m2を超えると粗雑なめつきとなり易
いので、Snめつき量は１ｇ／m2以下にしておく
ことが望ましい。
Sn／Cr2層めつき鋼板は、大気中の酸素により
Snめつき表面が酸化され易く、SnO、SnO2の成
長により変色して来る。また、塗装して使用する
場合には、SnO、SnO2の存在により塗料密着性
が著しく劣化する。したがつて、変色が問題とな
る用途や塗装して使用する用途の場合、Snめつ
き後に引き続いてクロメート被膜を施すことが好
ましい。
クロメート被膜層は金属CrとCr水和酸化物か
ら形成されることにより、優れた耐変色性と塗料
密着性が得られる。クロメート被膜層を形成させ
る方法は、10〜50ｇ／のCrO3と硫酸、硫酸塩、
フツ酸、フツ化物の１種または２種以上を含む浴
を用いて電流密度10A／ｄm2以上で行う。CrO3
濃度が50ｇ／を超えるとSnめつき層がエツチ
ングされるので好ましくない。またCrO3濃度10
ｇ／未満あるいは電流密度10A／ｄm2未満では
金属Crの析出が困難となる。
クロメート被膜量はCr換算で５〜30mg／m2で
ある。クロメート被膜量が５mg／m2未満では変色
防止効果および塗料密着性向上効果が不十分であ
り、30mg／m2超ではこれらの効果が飽和してしま
い不経済となる。クロメート被膜中の金属Crは
３mg／m2以上で塗料密着性向上効果が顕著である
が、20mg／m2以上になると金属Crは硬いのでス
リキズが入り易くなるので望ましくない。
本発明者らはさらに、本発明Snめつき浴中に
オキシエチレン鎖−［CH2CH2O−］o−を有する
界面活性剤、例えばエチレングリコール、ポリエ
チレングリコール、エチレングリコールモノメチ
ルエーテルなどのポリエチレングリコールアルキ
ルエーテル、エトキシレーテツドαナフトールな
どの芳香族エチレンオキサイドおよびポリエチレ
ングリコール脂肪酸エステル等を0.1〜10ｇ／
含有させることにより、外観色調の良い電気Cr
めつき上の電気Snめつきが得られることを知見
した。オキシエチレン鎖を有する界面活性剤濃度
が0.1ｇ／未満では外観色調を良くする効果が
無く、10ｇ／を越えると効果が飽和してしま
い、高価な界面活性剤を不必要に用いることにな
り、不経済である。ポリオキシエチレン鎖を有す
る界面活性剤は高価であるので、特に良い外観色
調を必要とする場合に使用することが望ましい。
＜実施例＞
次に、本発明の実施例および比較例について説
明する。
表１に本発明のSn／Cr2層めつき鋼板の製造方
法により製造した鋼板の実施例を示し、表２に比
較として用いた鋼板の製造方法を示した。表１、
表２に示す鋼板を用いて以下の試験を行つた。
その結果を表３に示す。
(1) めつき密着性は、90゜折り曲げ後、テープ剥
離試験を行い、
○ 剥離無し（０％）
× 剥離あり
で評価した。
(2) めつき外観色調は、目視判定により
○ 外観色調特に良
△ 外観色調良
× 外観色調不良
で評価した。
(3) 耐変色性は、210℃で５時間加熱した後の変
色の有無で評価した。
<Industrial Application Field> The present invention relates to a method for manufacturing a two-layer plated steel plate in which Cr and Sn are sequentially laminated on the surface of the steel plate. The present invention relates to a method for manufacturing a Sn/Cr double-layer plated steel sheet having a Sn/Cr double layer plating of 2 or less. <Prior art and its problems> When electrolytic Sn plating is applied to Cr metal plated by electroplating method, Cr metal remains on the Cr surface.
Due to the presence of hydrated oxides, satisfactory Sn plating cannot be achieved using conventional electro-Sn plating methods. In other words, electrochromium plating, which is usually carried out industrially, electrochemically converts Cr 6+ ions into metals.
It is reduced to Cr, but as is well known, Cr 6+
Ions are transferred to metal Cr via trivalent Cr hydrated oxide.
Cr hydrated oxide is always present on the plating surface, and this Cr hydrated oxide
This prevents Sn-glaring. Even if electrical Sn plating is applied in the presence of Cr hydrated oxide on the Cr metal surface, only a plated layer with poor adhesion will be obtained. Therefore, in order to apply electric Sn plating,
Cr hydrated oxide on the electroplated Cr surface must be removed. The method for removing this Cr hydrated oxide is as follows:
Method of dissolving with hot alkaline aqueous solution, NaOH
A method is known in which the material is dissolved by anodic electrolysis in an aqueous solution such as an aqueous solution, a phosphate buffer solution, or a borate buffer solution. In the method of dissolving with a hot alkaline aqueous solution, Cr oxide that is insoluble in alkali remains, making it impossible to provide satisfactory Sn plating. Furthermore, in anodic electrolytic treatment, metal Cr also dissolves, and hydrated Cr oxide remains until the metal Cr dissolves and disappears, so it cannot be used in the manufacturing method of Sn/Cr double-layer plated steel sheets. In addition, as a special pre-treatment for Sn plating, there is a prior art patent publication No. 33-1455 entitled ``Method for plating various metals on the surface of chromium and chromium alloys'', but the surface activation treatment disclosed in However, it is not possible to obtain Sn plating with practically satisfactory adhesion. Furthermore, there is a prior art patent publication No. 48-35136 entitled ``Chromium-tin double layer plating method'', but even with the disclosed Cr plating solution immersion treatment, Cr hydrated oxide on the Cr plated surface cannot be removed. is not completely removed,
Sufficient plating adhesion cannot be obtained. In addition, since the strike process is performed at a very high current density, there are problems such as difficulty in implementing the strike process due to equipment considerations. <Object of the invention> The object of the present invention is to provide a simple method for producing a Sn/Cr double-layer plated steel sheet that eliminates the above-mentioned conventional drawbacks, has excellent plating adhesion, good gloss, and discoloration resistance. It's about doing. According to the first aspect of the present invention, electricity is applied to the surface of the steel plate.
After applying Cr plating, wash with water and apply Sn ion 1.5 to 10.
Strongly acidic Sn containing g/ and a pH of less than 0.5 and 0 or more
Sn plating of 1 g/m 2 or less is performed using a plating bath at 20 to 50 A/dm 2 , and after washing with water, 10 to 50 g/m 2 is applied.
CrO 3 and sulfuric acid, sulfate, fluoric acid, fluoride 1
Using a bath containing one or more species at a current density of 10A/
A method for producing a Sn/Cr double-layer plated steel sheet is provided, which comprises forming a chromate coating layer consisting of metallic Cr and Cr hydrated oxide in an amount of 5 to 30 mg/m 2 in terms of dm 2 or more. According to the second aspect of the present invention, electricity is applied to the surface of the steel plate.
After applying Cr plating, wash with water and apply Sn ion 1.5 to 10.
g/ and a surfactant having an oxyethylene chain.
Using a strongly acidic Sn plating bath containing 0.1 to 10 g/ and a pH of less than 0.5 and 0 or more, 1 g/
After Sn plating of m2 or less and washing with water, 10 to 50
Current density using a bath containing g/g of CrO 3 and one or more of sulfuric acid, sulfate, hydrofluoric acid, and fluoride.
5 to 30 mg/m 2 of metal in terms of Cr at 10 A/dm 2 or more
A method for producing a Sn/Cr dual-layer plated steel sheet is provided, which is characterized by forming a chromate film layer consisting of Cr and Cr hydrated oxide. <Specific Structure of the Invention> The present invention will be described in more detail below. In the present invention, first, the surface of the steel plate is degreased by a conventional method.
After pickling, electric Cr plating is performed using a known Cr plating bath composition and plating conditions. Next, wash thoroughly with water, and then apply Sn ion 1.5 to 10
Sn plating is performed by cathodic electrolysis at 20 to 50 A/dm 2 in a strong acidic bath containing 20 to 50 A/dm 2 and a pH of less than 0.5 and 0 or more. Sn ions in the Sn plating bath in the present invention may be supplied using tin sulfate, tin chloride, tin borofluoride, tin pyrophosphate, tin fluoride, and other tin compounds, and the acids include sulfuric acid, hydrochloric acid, Inorganic acids such as hydrofluoric acid and boronic acid, or organic acids such as phenolsulfonic acid and cresolsulfonic acid may be used alone or in combination. In the Sn plating method of the present invention, a large amount of active H 2 gas is generated simultaneously with Sn plating. This large amount of active H2 gas completely removes the Cr hydrated oxide on the electroplated Cr surface, which could not be completely removed by conventional methods, and at the same time electrodeposit Sn, resulting in a close bond. This results in Sn plating superior to Cr plating with excellent properties. It is known that if plating is performed under conditions that involve a considerable amount of H 2 gas generation during Sn plating, the H 2 gas activates the steel sheet surface and a dense Sn plating layer is obtained. That is, in the areas disclosed in JP-B No. 19362-1972 "Electro-tin plating method" and JP-B No. 46-25603 "Acidic electro-tinning method", electro-Sn-plated steel sheets (commonly called tinplate) are used.
It has been shown that a low Sn ion concentration bath that generates a considerable amount of H 2 gas is used as a pretreatment to improve the corrosion resistance of steel. In some places, sulfate is added to a known tin sulfate bath or tin phenolsulfonate bath to form an extremely thin layer of Sn while generating H2 gas.
It is shown that plating is performed. However, these methods all involve Sn
This is a method for improving plating, in which Sn is added onto Cr plating where there is Cr hydrated oxide that inhibits plating.
It is not intended for plating, and the above method cannot provide satisfactory Sn plating on Cr plating.
In contrast, the manufacturing method of the present invention provides a method of Sn plating on Cr plating, which has been difficult in the past. As shown in Japanese Patent Application No. 59-117704 entitled "Surface-treated steel sheet with excellent weldability and manufacturing method thereof", the present inventors have already used hydrochloric acid, sulfuric acid, oxalic acid and acetic acid after electrochromic plating. Alternatively, it has been found that hydrated oxides on the electrically plated Cr surface can be efficiently removed by cathodic electrolysis in an aqueous solution containing two or more types. It has also been found that by containing tin ions in the aqueous solution, Sn plating can be applied at the same time as removing hydrated chromium oxide. As a result of further investigation into this acid solution containing Sn ions, the inventors found that
Suitable Sn for electrical Sn plating on Cr plating
The present invention was achieved by newly discovering ion concentration and hydrogen ion concentration (PH). The Sn ion concentration in the plating bath in the present invention is
The amount is 1.5 to 10 g/, more preferably 1.5 to 5 g/. If the Sn ion concentration is less than 1.5g/, Sn will not precipitate on the metal Cr, and if it exceeds 10g/, it will become powdery.
Otherwise, dendritic precipitation occurs, resulting in extremely poor appearance and impractical. The hydrogen ion concentration in the Sn plating bath in the present invention is less than 0.5 and 0 or more in terms of pH. If the hydrogen ion concentration is PH 0.5 or higher, the active H2 gas required to remove the Cr hydrated oxide on the electroplated Cr surface is insufficiently generated, resulting in Sn plating with insufficient adhesion. I can only get it. Also, when the pH is less than 0, active
Although the generation of H 2 gas is sufficient, the liquid becomes highly corrosive and excessive acid-proof measures must be taken for plating equipment, which is uneconomical. Plating current density is 20~
50 A/dm 2 is preferred. If it is less than 20 A/dm 2 , the generation efficiency of active H 2 gas is poor and it takes a long time for Sn plating, which is not preferable. If it exceeds 50 A/dm 2 , not only will the power supply become expensive, but also the plating solution will generate heat due to the Joule heat, which is undesirable. The preferred range of plating temperature is 30 to 50°C. In this Sn plating method, which generates a large amount of H 2 gas, if the Sn plating amount exceeds 1 g/m 2 , it tends to result in rough plating, so it is desirable to keep the Sn plating amount below 1 g/m 2 . Sn/Cr double-layer plated steel sheets are exposed to oxygen in the atmosphere.
The Sn-plated surface is easily oxidized and becomes discolored due to the growth of SnO and SnO 2 . Furthermore, when used after painting, the presence of SnO and SnO 2 significantly deteriorates paint adhesion. Therefore, in applications where discoloration is a problem or applications where the material is to be painted, it is preferable to apply a chromate film after Sn plating. The chromate coating layer is formed from metal Cr and Cr hydrated oxide, providing excellent discoloration resistance and paint adhesion. The method for forming the chromate film layer is to use 10 to 50 g/CrO 3 and sulfuric acid, sulfate,
The process is carried out at a current density of 10 A/dm 2 or more using a bath containing one or more of fluoric acid and fluoride. CrO3
If the concentration exceeds 50 g/l, the Sn plating layer will be etched, which is not preferable. Also CrO3 concentration 10
If the current density is less than 10 A/dm 2 or less than 10 A/dm 2 , precipitation of metal Cr becomes difficult. The amount of chromate coating is 5 to 30 mg/m 2 in terms of Cr. If the amount of chromate coating is less than 5 mg/m 2 , the effect of preventing discoloration and the effect of improving paint adhesion is insufficient, and if it exceeds 30 mg/m 2 , these effects become saturated and become uneconomical. If the metal Cr in the chromate film is 3 mg/m 2 or more, the effect of improving paint adhesion is remarkable, but if it is 20 mg/m 2 or more, the metal Cr is hard and becomes susceptible to scratches, which is not desirable. The present inventors further added that surfactants having an oxyethylene chain -[ CH2CH2O- ] o- , such as polyethylene glycols such as ethylene glycol, polyethylene glycol, and ethylene glycol monomethyl ether, are used in the Sn plating bath of the present invention. Aromatic ethylene oxide such as alkyl ether, ethoxylated α-naphthol, polyethylene glycol fatty acid ester, etc. at 0.1 to 10 g/
By containing electric Cr, it has a good appearance color tone.
It was discovered that electric Sn plating on plating can be obtained. If the concentration of the surfactant having an oxyethylene chain is less than 0.1 g/l, it will not have the effect of improving the appearance color tone, and if it exceeds 10 g/l, the effect will be saturated and expensive surfactants will be used unnecessarily. It is uneconomical. Since surfactants having polyoxyethylene chains are expensive, it is desirable to use them when particularly good appearance color tone is required. <Examples> Next, examples and comparative examples of the present invention will be described. Table 1 shows examples of steel sheets manufactured by the Sn/Cr double-layer plated steel sheet manufacturing method of the present invention, and Table 2 shows the manufacturing method of steel sheets used for comparison. Table 1,
The following tests were conducted using the steel plates shown in Table 2. The results are shown in Table 3. (1) Plating adhesion was evaluated by performing a tape peeling test after bending at 90° and evaluating it as follows: ○ No peeling (0%) x Peeling. (2) The plating appearance color tone was visually evaluated as ○, appearance color is particularly good, △, appearance color is good, and appearance color is poor. (3) Discoloration resistance was evaluated by the presence or absence of discoloration after heating at 210°C for 5 hours.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
＜発明の効果＞
表１、表２、表３により本発明の製造法による
Sn／Cr2層めつき鋼板は優れためつき密着性と良
い外観色調を有し、しかも耐変色性が強いことが
分る。[Table] <Effects of the invention> Tables 1, 2, and 3 show that the production method of the present invention
It can be seen that the Sn/Cr dual-layer plated steel sheet has excellent mating adhesion and good appearance color tone, and has strong discoloration resistance.
Claims (1)
し、Snイオン1.5〜10ｇ／を含みPHが0.5未満０
以上である強酸性Snめつき浴を用いて20〜50A／
ｄm2で１ｇ／m2以下のSnめつきを行い、水洗し
た後、10〜50ｇ／のCrO3と硫酸、硫酸塩、フ
ツ酸、フツ化物の１種または２種以上を含む浴を
用い電流密度10A／ｄm2以上でCr換算で５〜30
mg／m2の金属CrとCr水和酸化物から成るクロメ
ート被膜層を形成させることを特徴とするSn／
Cr2層めつき鋼板の製造方法。 ２ 鋼板表面に電気Crめつきを施した後、水洗
し、Snイオン1.5〜10ｇ／とオキシエチレン鎖
を有する界面活性剤を0.1〜10ｇ／を含みPHが
0.5未満０以上である強酸性Snめつき浴を用いて
20〜50A／ｄm2で１ｇ／m2以下のSnめつきを行
い、水洗した後、10〜50ｇ／のCrO3と硫酸、
硫酸塩、フツ酸、フツ化物の１種または２種以上
を含む浴を用い電流密度10A／ｄm2以上でCr換算
で５〜30mg／m2の金属CrとCr水和酸化物から成
るクロメート被膜層を形成させることを特徴とす
るSn／Cr2層めつき鋼板の製造方法。[Claims] 1. After applying electric chromium plating to the surface of the steel plate, it is washed with water and contains 1.5 to 10 g of Sn ions and has a pH of less than 0.5.
20~50A/
After performing Sn plating of 1 g/m 2 or less in dm 2 and washing with water, electric current is applied using a bath containing 10 to 50 g/m of CrO 3 and one or more of sulfuric acid, sulfate, hydrofluoric acid, and fluoride. Density 10A/dm2 or more , 5 to 30 in Cr conversion
Sn /
Manufacturing method of Cr double-layer plated steel plate. 2 After applying electric chromium plating to the surface of the steel sheet, it is washed with water, and the PH is
Using a strongly acidic Sn plating bath with a value of less than 0.5 and more than 0
After performing Sn plating of 1 g/m 2 or less at 20-50 A/dm 2 and washing with water, 10-50 g/CrO 3 and sulfuric acid,
A chromate coating consisting of metal Cr and Cr hydrated oxide with a current density of 10 A/dm 2 or higher and a concentration of 5 to 30 mg/m 2 in terms of Cr using a bath containing one or more of sulfate, fluoric acid, and fluoride. A method for manufacturing a Sn/Cr double-layer plated steel sheet, which is characterized by forming a layer.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59252355A JPS61130500A (en) | 1984-11-29 | 1984-11-29 | Production of sn/cr two-layered plated steel plate |
| AU50366/85A AU559801B2 (en) | 1984-11-29 | 1985-11-26 | Surface treated steel strip |
| EP85114989A EP0184115B1 (en) | 1984-11-29 | 1985-11-26 | Surface-treated steel strip having improved weldability and process for making |
| DE8585114989T DE3568356D1 (en) | 1984-11-29 | 1985-11-26 | Surface-treated steel strip having improved weldability and process for making |
| ZA859071A ZA859071B (en) | 1984-11-29 | 1985-11-27 | Surface-treated steel strip having improved weldability and process for making |
| CN85109305A CN1006694B (en) | 1984-11-29 | 1985-11-28 | Surface treated steel strip having improved weldability and process for making |
| KR1019850008916A KR900001829B1 (en) | 1984-11-29 | 1985-11-28 | Surace-treated steel strip having improved weldability and process for making |
| CA000496616A CA1273600A (en) | 1984-11-29 | 1985-11-29 | Surface-treated steel strip having improved weldability and process for making |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59252355A JPS61130500A (en) | 1984-11-29 | 1984-11-29 | Production of sn/cr two-layered plated steel plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61130500A JPS61130500A (en) | 1986-06-18 |
| JPH052744B2 true JPH052744B2 (en) | 1993-01-13 |
Family
ID=17236135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59252355A Granted JPS61130500A (en) | 1984-11-29 | 1984-11-29 | Production of sn/cr two-layered plated steel plate |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0184115B1 (en) |
| JP (1) | JPS61130500A (en) |
| KR (1) | KR900001829B1 (en) |
| CN (1) | CN1006694B (en) |
| AU (1) | AU559801B2 (en) |
| CA (1) | CA1273600A (en) |
| DE (1) | DE3568356D1 (en) |
| ZA (1) | ZA859071B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4563399A (en) * | 1984-09-14 | 1986-01-07 | Michael Ladney | Chromium plating process and article produced |
| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
| JPS6376896A (en) * | 1986-09-18 | 1988-04-07 | Nippon Steel Corp | Production of surface-treated steel sheet having excellent seam weldability and corrosion resistance |
| JPH01191772A (en) * | 1988-01-26 | 1989-08-01 | Toyo Kohan Co Ltd | Production of plated steel sheet for can having excellent working corrosion resistance |
| JP2707884B2 (en) * | 1991-09-06 | 1998-02-04 | 日本鋼管株式会社 | Method for producing multi-layer electrolytic chromate treated steel sheet |
| KR20020050383A (en) * | 2000-12-21 | 2002-06-27 | 이구택 | A producing process for surface-treated steel sheet with superior weldability |
| CN1313470C (en) * | 2004-02-11 | 2007-05-02 | 上海新先锋药业有限公司 | N-methyl benzothiazole lifumeisu and method for preparing same |
| CN101015971B (en) * | 2007-02-05 | 2011-05-11 | 蒋彩峰 | Steel plate type novel decorative plate and manufacture method |
| CN102191513B (en) * | 2011-04-28 | 2012-08-22 | 北京化工大学 | Preparation method of insoluble titanium-based catalytic electrode |
| ES2583372T3 (en) * | 2012-03-30 | 2016-09-20 | Tata Steel Ijmuiden Bv | Coated substrate for packaging applications and a method of producing said coated substrate |
| CN104936738B (en) * | 2013-01-29 | 2018-12-18 | 大日制罐株式会社 | Weld the manufacturing method of tank body, welded tank, the manufacturing method for welding tank body and welded tank |
| CN103921499B (en) * | 2014-04-22 | 2017-02-15 | 刘建忠 | Metal material with excellent soldering performance |
| CN110885999A (en) * | 2018-09-10 | 2020-03-17 | 上海梅山钢铁股份有限公司 | Chromic acid passivation method for cold-rolled electroplated tin steel plate |
| CN113529141B (en) * | 2021-06-17 | 2022-11-18 | 首钢集团有限公司 | Tin-chromium composite coating steel plate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190597A (en) * | 1984-03-09 | 1985-09-28 | Toyo Kohan Co Ltd | Surface treated steel sheet for welded can and its production |
| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2465011A1 (en) * | 1979-09-06 | 1981-03-20 | Carnaud Sa | MATERIAL CONSISTING OF A PROTECTED STEEL SHEET, METHOD FOR MANUFACTURING SAME, AND APPLICATIONS THEREOF, IN PARTICULAR TO PRESERVE BOXES |
| JPS59170298A (en) * | 1983-03-15 | 1984-09-26 | Kawasaki Steel Corp | Manufacture of tin-free steel sheet with superior adhesion to paint |
-
1984
- 1984-11-29 JP JP59252355A patent/JPS61130500A/en active Granted
-
1985
- 1985-11-26 AU AU50366/85A patent/AU559801B2/en not_active Ceased
- 1985-11-26 EP EP85114989A patent/EP0184115B1/en not_active Expired
- 1985-11-26 DE DE8585114989T patent/DE3568356D1/en not_active Expired
- 1985-11-27 ZA ZA859071A patent/ZA859071B/en unknown
- 1985-11-28 CN CN85109305A patent/CN1006694B/en not_active Expired
- 1985-11-28 KR KR1019850008916A patent/KR900001829B1/en not_active IP Right Cessation
- 1985-11-29 CA CA000496616A patent/CA1273600A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60190597A (en) * | 1984-03-09 | 1985-09-28 | Toyo Kohan Co Ltd | Surface treated steel sheet for welded can and its production |
| JPS61130500A (en) * | 1984-11-29 | 1986-06-18 | Kawasaki Steel Corp | Production of sn/cr two-layered plated steel plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1273600A (en) | 1990-09-04 |
| EP0184115B1 (en) | 1989-02-22 |
| DE3568356D1 (en) | 1989-03-30 |
| EP0184115A1 (en) | 1986-06-11 |
| AU5036685A (en) | 1986-06-05 |
| KR860004165A (en) | 1986-06-18 |
| CN85109305A (en) | 1986-08-06 |
| JPS61130500A (en) | 1986-06-18 |
| ZA859071B (en) | 1986-07-30 |
| KR900001829B1 (en) | 1990-03-24 |
| CN1006694B (en) | 1990-02-07 |
| AU559801B2 (en) | 1987-03-19 |
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