JPH0351797B2 - - Google Patents
Info
- Publication number
- JPH0351797B2 JPH0351797B2 JP60158016A JP15801685A JPH0351797B2 JP H0351797 B2 JPH0351797 B2 JP H0351797B2 JP 60158016 A JP60158016 A JP 60158016A JP 15801685 A JP15801685 A JP 15801685A JP H0351797 B2 JPH0351797 B2 JP H0351797B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- aqueous solution
- aluminum alloy
- steel sheet
- plated steel
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 229910000831 Steel Inorganic materials 0.000 claims description 25
- 239000010959 steel Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 20
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 20
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910001430 chromium ion Inorganic materials 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 239000003973 paint Substances 0.000 claims description 8
- 238000010422 painting Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000008397 galvanized steel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 229910052804 chromium Inorganic materials 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 phenolic carboxylic acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910007572 Zn-K Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
〔産業上の利用分野〕
本発明はアルミニウム含有量が１〜70％の亜鉛
−アルミニウム合金めつき鋼板の表面処理方法に
関するものである。
〔従来の技術〕
従来より亜鉛めつき鋼板を塗装するに際し、６
価クロム化合物を主剤としたクロメート水溶液で
亜鉛めつき鋼板を処理してクロメート皮膜を化成
させて塗装下地性を向上させることが良く知られ
ている。最近公害上の問題から６価クロム含有水
を工場外に排出することが出来なくなつたので、
亜鉛めつき鋼板に６価クロム及びシリカを含む酸
性の塗布型クロメート水溶液を塗布して水洗する
ことなくそのまま乾燥して塗装下地とするクロメ
ート処理法がとられるようになつた。
近年めつき鋼板自体の耐食性を向上させる為
種々の合金めつき鋼板が開発されているが、その
中で亜鉛−アルミニウム合金めつき鋼板が注目さ
れ市場にも出ている。この亜鉛−アルミニウム合
金めつきはめつき皮膜中に１〜70％のアルミニウ
ムを含有させるもので、従来の溶融亜鉛めつきに
比較して裸めつき板の耐食性が格段に良好にな
る。しかし、この亜鉛−アルミニウム合金めつき
鋼板に前記塗布型のクロメート水溶液にて塗装下
地皮膜を形成させてもその効果は余りなく、３年
間屋外曝露後の前記合金めつき鋼板の切断部の塗
装ふくれ状態を観察すると無処理と殆ど差がなか
つた。
〔発明が解決しようとする問題点〕
本発明は亜鉛−アルミニウム合金めつき鋼板表
面に塗布型クロメート水溶液を塗布する前に表面
調整を行つて、従来のクロメート塗布法よりも屋
外曝露性を向上させることを目的としている。
〔問題点を解決するための手段〕
本発明者は、前記目的を達成させる為に、塗布
型クロメート処理するにあたり予め亜鉛−アルミ
ニウム合金めつき鋼板表面のアルミニウムを選択
的に除去することを検討した。その結果亜鉛−ア
ルミニウム合金めつき鋼板を金属イオン、特にコ
バルト、鉄、ニツケル、マンガンの１種又は２種
以上の金属イオンを含み且つ該金属イオンが溶存
するに必要な量の錯化剤を含むPH13.5以上のアル
カリ水溶液で前処理することにより、該めつき鋼
板表面に偏析濃化していたアルミニウムを除去
し、その後シリカを含む塗布型クロメート水溶液
を塗布することにより本発明の目的を達成させる
ことが出来た。又その後塗装するのであるが、下
塗塗料としてエポキシ樹脂塗料を用いると、他の
塗料に比べ屋外曝露型が更に優れていることがわ
かつた。
本発明に於けるアルカリ水溶液に含まれる金属
イオンは硝酸塩、硫酸塩、炭酸塩、塩化物等の無
機塩、その他水溶液又はアルカリに可溶な化合物
として供給する。その濃度は金属換算で0.01〜10
ｇ／、好ましくは0.05〜５ｇ／である。そし
てこれらの金属イオンがアルカリ水溶液中で溶存
状態で維持されるように錯化剤で充分錯化されて
いなければならないが、その錯化剤は通常0.1〜
20ｇ／の濃度で使い、その錯化剤としては縮合
りん酸塩、アンモニア等の無機錯化剤、そして有
機錯化剤としてマロン酸、フマル酸等のようなジ
カルボン酸、グリシンのようなアミノ酸類、クエ
ン酸、グルコン酸、乳酸のようなヒドロキシカル
ボン酸類、ソルビトール、１−２エタンジオール
のようなポリヒドロキシ脂肪族化合物、サリチル
酸、フタル酸のようなフエノールカルボン酸類、
エチレンジアミンテトラ酢酸のようなアミンカル
ボン酸類、ジエタノールアミノメタンホスホネー
トのようなポリアミノ酸、リグノスルホン酸塩類
などである。特に好ましくはヘキサヒドロキシヘ
プトン酸、グルコン酸ナトリウム、エチレンジア
ミンテトラ酢酸のナトリウム塩である。
本発明に於ける処理工程は、亜鉛−アルミニウ
ム合金めつき鋼板をスプレー又は浸漬法に依つて
本発明に於ける常温〜沸騰温度のアルカリ水溶液
で前記めつき鋼板表面のアルミニウムを選択的に
エツチング除去するに必要な時間処理し、水洗後
シリカを含んだクロメート水溶液にて塗布する工
程からなる。本発明に於けるアルカリ水溶液によ
る実用上満足な前処理としては連続フープライン
の場合、通常処理温度50〜80℃、処理時間４〜10
秒で行われるが、高温高濃度のアルカリ水溶液を
用いれば更に短時間でも処理可能である。本発明
に於けるシリカを含むクロメート水溶液の亜鉛−
アルミニウム合金めつき鋼板表面に対する塗布量
は乾燥温度で10〜400mg／m2である。10mg／m2未
満だと本発明の効果を発揮するのに充分でなく、
400mg／m2より上まわると塗料付着性を低下させ
て実用的でない。
クロメート水溶液中の６価クロムイオンは無水
クロム酸から誘導され、シリカとしてはコロイダ
ルシリカから誘導される。又クロメート水溶液に
３価クロムイオン及び／又はリン酸イオンが含ま
れるのが好ましい。３価クロムは、６価クロムを
含有するクロメート水溶液に、でんぷん、しゆう
酸、タンニン、アルコール等の還元剤を添加する
ことによつて含有させる。クロメート水溶液中の
シリカ／６価クロムイオン重量比は0.6〜15が好
ましい。クロメート水溶液中の３価クロムイオ
ン／６価クロムイオン重量比は0.2〜１が好まし
い。クロメート水溶液中のPO4／６価クロムイオ
ン重量比は0.6〜３が好ましい。
〔作用〕
本発明に於けるアルカリ水溶液の亜鉛−アルミ
ニウム合金めつき鋼板表面のアルミニウムの選択
エツチング性について行つた試験例を示す。
試験例
「スーパージンク」の商標で市販されている亜
鉛−アルミニウム合金（Zn90〜96.5％、Al3.5〜
10％）めつき鋼板を第１表記載のPH13.5〜13.7の
処理液で浴温57〜63℃にて５秒間スプレー処理し
た。鉄はFe（NO3）3を、ニツケルはNi（NO3）2と
して、コバルトはCo（NO3）2として使用した。そ
れぞれの金属イオンの濃度は使用した薬剤の金属
換算値である。処理後水洗乾燥し、この処理板の
表面を蛍光Ｘ分析装置（FXA）にてAl−K〓を管
球：Cr、分光結晶：EDDT、電圧50KV、電流30
ｍＡ、積分時間20秒で、またZn−K〓を管球：Ｗ、
分光結晶：LiF、電圧20KV、電流２ｍＡ、積分
時間10秒の条件で測定し、Alのカウント及びZn
のカウントからAl／Znを算出した。その結果を
第１表に示す。
[Industrial Field of Application] The present invention relates to a method for surface treatment of a zinc-aluminum alloy plated steel sheet having an aluminum content of 1 to 70%. [Conventional technology] Conventionally, when painting galvanized steel sheets, 6
It is well known that a galvanized steel sheet is treated with a chromate aqueous solution containing a chromium compound as the main ingredient to chemically form a chromate film and thereby improve the base properties for painting. Recently, due to pollution problems, it has become impossible to discharge water containing hexavalent chromium outside the factory.
A chromate treatment method has come into use in which a galvanized steel sheet is coated with an acidic coating-type chromate aqueous solution containing hexavalent chromium and silica, and then dried without washing with water to serve as a base for painting. In recent years, various alloy-plated steel sheets have been developed in order to improve the corrosion resistance of the plated steel sheets themselves, and among these, zinc-aluminum alloy-plated steel sheets have attracted attention and are now on the market. This zinc-aluminum alloy plating contains 1 to 70% aluminum in the plating film, and the corrosion resistance of the bare plated plate is much better than that of conventional hot-dip galvanizing. However, even if a coating base film is formed on this zinc-aluminum alloy plated steel sheet with the above-mentioned paint-type chromate aqueous solution, the effect is not so great, and the paint blisters on the cut portion of the alloy-plated steel sheet after three years of outdoor exposure. When the condition was observed, there was almost no difference from the untreated condition. [Problems to be Solved by the Invention] The present invention improves outdoor exposure properties compared to conventional chromate coating methods by performing surface conditioning before applying a coated chromate aqueous solution to the surface of a zinc-aluminum alloy coated steel sheet. The purpose is to [Means for Solving the Problems] In order to achieve the above object, the present inventor has considered selectively removing aluminum on the surface of a zinc-aluminum alloy plated steel sheet in advance of coating-type chromate treatment. . As a result, the zinc-aluminum alloy plated steel sheet contains metal ions, particularly one or more metal ions of cobalt, iron, nickel, and manganese, and also contains a complexing agent in an amount necessary for dissolving the metal ions. The purpose of the present invention is achieved by pre-treating with an alkaline aqueous solution with a pH of 13.5 or higher to remove the aluminum that has been segregated and concentrated on the surface of the galvanized steel sheet, and then applying a coating type chromate aqueous solution containing silica. I was able to do it. Furthermore, when painting is performed afterwards, it was found that when an epoxy resin paint is used as an undercoat, the outdoor exposure type is even better than other paints. The metal ions contained in the alkaline aqueous solution in the present invention are supplied as inorganic salts such as nitrates, sulfates, carbonates, chlorides, and other compounds soluble in the aqueous solution or alkali. Its concentration is 0.01 to 10 in metal terms
g/, preferably 0.05 to 5 g/. These metal ions must be sufficiently complexed with a complexing agent so that they can be maintained in a dissolved state in the alkaline aqueous solution.
It is used at a concentration of 20g/, and the complexing agents are inorganic complexing agents such as condensed phosphates and ammonia, and the organic complexing agents are dicarboxylic acids such as malonic acid and fumaric acid, and amino acids such as glycine. , hydroxycarboxylic acids such as citric acid, gluconic acid, and lactic acid; polyhydroxy aliphatic compounds such as sorbitol and 1-2 ethanediol; phenolic carboxylic acids such as salicylic acid and phthalic acid;
These include amine carboxylic acids such as ethylenediaminetetraacetic acid, polyamino acids such as diethanolaminomethanephosphonate, and lignosulfonates. Particularly preferred are sodium salts of hexahydroxyheptonic acid, sodium gluconate, and ethylenediaminetetraacetic acid. The treatment step in the present invention involves selectively etching and removing aluminum on the surface of a zinc-aluminum alloy plated steel plate with an alkaline aqueous solution at room temperature to boiling temperature using a spraying or dipping method. The process consists of processing for the required time, washing with water, and then coating with a chromate aqueous solution containing silica. In the case of a continuous hoop line, a practically satisfactory pretreatment with an alkaline aqueous solution in the present invention is usually performed at a treatment temperature of 50 to 80℃ and a treatment time of 4 to 10℃.
Although the process takes seconds, it is possible to perform the process in a shorter time by using a high-temperature, high-concentration alkaline aqueous solution. Zinc in the chromate aqueous solution containing silica in the present invention
The amount applied to the surface of the aluminum alloy plated steel plate is 10 to 400 mg/m 2 at drying temperature. If it is less than 10mg/m2, it is not sufficient to exhibit the effect of the present invention.
If it exceeds 400 mg/m 2 , paint adhesion deteriorates and is not practical. The hexavalent chromium ion in the chromate aqueous solution is derived from chromic anhydride, and the silica is derived from colloidal silica. Further, it is preferable that the aqueous chromate solution contains trivalent chromium ions and/or phosphate ions. Trivalent chromium is contained by adding a reducing agent such as starch, oxalic acid, tannin, or alcohol to a chromate aqueous solution containing hexavalent chromium. The silica/hexavalent chromium ion weight ratio in the chromate aqueous solution is preferably 0.6 to 15. The trivalent chromium ion/hexavalent chromium ion weight ratio in the chromate aqueous solution is preferably 0.2 to 1. The weight ratio of PO 4 /hexavalent chromium ion in the chromate aqueous solution is preferably 0.6 to 3. [Function] An example of a test conducted on the selective etching of aluminum on the surface of a zinc-aluminum alloy plated steel plate using an alkaline aqueous solution according to the present invention will be described. Test example Zinc-aluminum alloy (Zn90~96.5%, Al3.5~
(10%) plated steel plate was spray treated with a treatment solution having a pH of 13.5 to 13.7 listed in Table 1 for 5 seconds at a bath temperature of 57 to 63°C. Fe(NO 3 ) 3 was used for iron, Ni(NO 3 ) 2 was used for nickel, and Co(NO 3 ) 2 was used for cobalt. The concentration of each metal ion is the metal equivalent value of the drug used. After the treatment, the surface of the treated plate was washed with water and dried, and the surface of this treated plate was analyzed with Al-K– using a fluorescence X analyzer (FXA), tube: Cr, spectroscopic crystal: EDDT, voltage 50KV, current 30
mA, integration time 20 seconds, and Zn-K〓 tube: W,
Spectroscopic crystal: LiF, measured under the conditions of voltage 20KV, current 2mA, and integration time 10 seconds, counting Al and Zn.
Al/Zn was calculated from the count. The results are shown in Table 1.
【表】
第１表から明らかな如く無処理に比べ本発明に
於けるアルカリ水溶液（No.１、No.２、No.３）で処
理したものは亜鉛−アルミニウム合金めつき鋼板
のAl量が減少していることが分かる。
実施例 １
「スーパージンク」の商標で市販されている亜
鉛−アルミニウム合金めつき鋼板を、Fe（NO3）3
をFe換算で0.17ｇ／、Ni（NO3）2をNi換算で
0.24ｇ／、ヘキサヒドロキシヘプトンソーダを
1.7ｇ／、苛性ソーダ22ｇ／含有するPH13.6、
液温57〜63℃のアルカリ水溶液で10秒間スプレー
処理し、水洗し、６価クロム17.7ｇ／含有する
水溶性クロム化合物中に３価クロム9.9ｇ／含
有し、シリカ15.8ｇ／を含んだPH３の液でロー
ルコーター塗布し乾燥して190mg／m2の皮膜を得
た。
比較例１としては、溶融亜鉛めつき鋼板及び亜
鉛−アルミニウム合金めつき鋼板の無処理と、そ
れ等の鋼板にアルカリ水溶液による処理を除いた
以外は実施例１と同一条件で処理した。
実施例 ２
実施例１と同様の亜鉛−アルミニウム合金めつ
き鋼板を、Fe（NO3）3をFe換算で0.17ｇ／、Co
（NO3）2をCo換算で0.24ｇ／、ヘキサヒドロキ
シヘプトンソーダを1.7ｇ／、苛性ソーダ22
ｇ／含有するPH13.6、液温55〜60℃のアルカリ
水溶液で６秒間スプレー処理し、水洗し、６価ク
ロム16.5ｇ／含有する水溶液クロム化合物中に
３価クロム9.9ｇ／及びシリカ54.2ｇ／を含
有し、更にPO425.5ｇ／を含んだPH1.5の液でロ
ールコーター塗布し乾燥して280mg／m2の皮膜を
得た。
比較例２して、溶融亜鉛めつき鋼板及び亜鉛−
アルミニウム合金めつき鋼板にアルカリ水溶液に
よる処理を除いた以外は実施例２と同一条件で処
理した。
前記処理された合金めつき鋼板に、２コートの
ものはエポキシ系下塗塗料を膜厚5μになるよう
にバーコーターで塗布し、処理温度190℃で焼付
け、次いでポリエステル系上塗塗料を13μになる
ようにバーコーターで塗布し、処理温度が200℃
で焼付けた。また１コートのものはポリエステル
系１コート塗料を14μになるようにバーコーター
で塗布し、処理温度210℃で焼付けた。その塗装
板について塗膜密着性及び耐食性試験を行つた結
果を第２表に示す。[Table] As is clear from Table 1, the amount of Al in the zinc-aluminum alloy coated steel sheets treated with the alkaline aqueous solution (No. 1, No. 2, No. 3) of the present invention was lower than that of the untreated sheet. It can be seen that it is decreasing. Example 1 A zinc-aluminum alloy plated steel sheet commercially available under the trademark “Super Zinc” was treated with Fe(NO 3 ) 3
0.17g/ in terms of Fe, Ni(NO 3 ) 2 in terms of Ni
0.24g/hexahydroxyheptone soda
1.7g/, caustic soda 22g/contains PH13.6,
Spray treated with an alkaline aqueous solution at a liquid temperature of 57 to 63°C for 10 seconds and washed with water to obtain PH3 containing 17.7 g of hexavalent chromium/9.9 g of trivalent chromium in the water-soluble chromium compound and 15.8 g of silica. The solution was applied using a roll coater and dried to obtain a film of 190 mg/m 2 . Comparative Example 1 was treated under the same conditions as Example 1, except that the hot-dip galvanized steel sheet and the zinc-aluminum alloy coated steel sheet were not treated, and the steel sheets were not treated with an alkaline aqueous solution. Example 2 A zinc-aluminum alloy coated steel sheet similar to Example 1 was coated with Fe(NO 3 ) 3 of 0.17 g/Co in terms of Fe.
(NO 3 ) 2 in terms of Co 0.24g/, hexahydroxyheptone soda 1.7g/, caustic soda 22
g/sprayed for 6 seconds with an alkaline aqueous solution with a pH of 13.6 and a liquid temperature of 55 to 60°C, washed with water, 16.5 g of hexavalent chromium/9.9 g of trivalent chromium in the aqueous chromium compound contained/and 54.2 g of silica. A liquid with a pH of 1.5 containing 25.5 g of PO 4 was coated with a roll coater and dried to obtain a film of 280 mg/m 2 . Comparative Example 2, hot-dip galvanized steel sheet and zinc-
The aluminum alloy-plated steel sheet was treated under the same conditions as in Example 2, except that the treatment with an alkaline aqueous solution was omitted. For two coats, epoxy undercoat is applied to the alloy-plated steel sheet treated above to a thickness of 5μ using a bar coater, baked at a treatment temperature of 190°C, and then polyester topcoat is applied to a thickness of 13μ. coated with a bar coater, and the processing temperature was 200℃.
Burnt with. For the one-coat type, a one-coat polyester paint was applied to a thickness of 14μ using a bar coater, and baked at a processing temperature of 210°C. Table 2 shows the results of coating film adhesion and corrosion resistance tests on the coated plates.
【表】
試験方法は次の如く行つた。
(1) 折り曲げ試験、衝撃試験
折り曲げ試験は塗装後試験板を二つ折りにし
て折り曲げ部分に試験板と同厚みの板片を２枚
折り曲げ部に挿入し万力を用いて締めつけ、折
り曲げた面にスコツチテープを貼りテープを急
激に剥がす。本試験後折り曲げ面に対する塗膜
の剥離面積より評価点をつける。
衝撃試験はデユポン式衝撃試験機によつて撃
心1/2″、荷重１Kg、高さ50cmで行い、凹面にス
コツチテープを貼りテープを急激に剥がす。本
試験後凹面に対する塗膜の剥離面積により評価
点をつける。評価点の区別は次の通りである。[Table] The test method was as follows. (1) Bending test, impact test For the bending test, after painting, the test plate is folded in half, two pieces of the same thickness as the test plate are inserted into the folded part, tightened using a vise, and the folded surface is Apply Scotch tape and peel off the tape rapidly. After this test, an evaluation score is given based on the peeled area of the coating film on the bent surface. The impact test was conducted using a Dupont impact tester with a center of impact of 1/2", a load of 1 kg, and a height of 50 cm. Scotchi tape was applied to the concave surface and the tape was rapidly peeled off. After the test, evaluation was made by the peeled area of the paint film on the concave surface. Assign points.The evaluation points are as follows.
【表】
(2) コインスクラツチ試験
10円硬貨により塗面をひつかく。本試験後試
験面に塗膜の剥離面積により評価点をつける。
評価点の区別は次の通りである。[Table] (2) Coin scratch test Scratch the painted surface with a 10 yen coin. After this test, an evaluation score will be given to the test surface based on the peeled area of the paint film.
The evaluation points are distinguished as follows.
【表】
(3) 耐食性試験
３−１ ５％の塩水噴霧試験
塗装後試験板にナイフで塗面を通して素地
に達する傷を入れた部分、切断部及び折り曲
げ部についてJIS−Ｚ−2371により５％塩水
噴霧試験、１コートの場合：500時間、２コ
ートの場合：1000時間行い、下記の判定基準
により判定する。
３−２ 屋外曝露試験
神奈川県の住宅地に３年間曝露した。[Table] (3) Corrosion resistance test 3-1 5% salt spray test 5% according to JIS-Z-2371 for the parts where the test plate is scratched by passing a knife through the coated surface to the base, cut parts and bent parts after painting. Salt spray test: 1 coat: 500 hours, 2 coats: 1000 hours, and judged according to the following criteria. 3-2 Outdoor exposure test Tests were exposed to a residential area in Kanagawa Prefecture for 3 years.
以上の如く、アルミニウム含有量が１〜70％の
亜鉛−アルミニウム合金めつき鋼板に、コロイダ
ルシリカを含むクロメート水溶液を塗布する前に
本発明に於けるアルカリ水溶液にて処理すること
により、塗装後の屋外曝露性を向上させることが
出来る。
As described above, by treating a zinc-aluminum alloy plated steel sheet with an aluminum content of 1 to 70% with the alkaline aqueous solution of the present invention before applying a chromate aqueous solution containing colloidal silica, Outdoor exposure can be improved.
Claims (1)
−アルミニウム合金めつき鋼板にニツケル、鉄、
コバルト、マンガンの群より選ばれた１種又は２
種以上の金属イオン及び該金属イオンを溶存させ
るに必要な量の錯化剤を含むPH13.5以上のアルカ
リ水溶液にて処理を施し、前記亜鉛−アルミニウ
ム合金表面のアルミニウムを選択的に除去し、次
いでコロイダルシリカを含み該シリカの６価クロ
ムイオンに対する重量比が0.6〜15であり、３価
クロムイオンの６価クロムイオンに対する重量比
が0.2〜１であるクロメート水溶液を塗布して乾
燥し、10〜400mg／m2の皮膜を形成させた後塗装
することを特徴とする亜鉛−アルミニウム合金め
つき鋼板の表面処理方法。 ２ 前記クロメート水溶液にリン酸イオンを含み
リン酸イオンの６価クロムイオンに対する重量比
が0.6〜３であることを特徴とする特許請求の範
囲第１項記載の亜鉛−アルミニウム合金めつき鋼
板の表面処理方法。 ３ 塗装において下塗り塗料としてエポキシ樹脂
塗料を施すことを特徴とする特許請求の範囲第１
項記載の亜鉛−アルミニウム合金めつき鋼板の表
面処理方法。[Claims] 1 A zinc-aluminum alloy coated steel sheet with an aluminum content of 1 to 70% by weight, nickel, iron,
One or two selected from the group of cobalt and manganese
selectively removing aluminum on the surface of the zinc-aluminum alloy by treating with an alkaline aqueous solution with a pH of 13.5 or higher containing at least one metal ion and a complexing agent in an amount necessary to dissolve the metal ion; Next, a chromate aqueous solution containing colloidal silica and having a weight ratio of silica to hexavalent chromium ions of 0.6 to 15 and a weight ratio of trivalent chromium ions to hexavalent chromium ions of 0.2 to 1 is applied and dried. A method for surface treatment of a zinc-aluminum alloy plated steel sheet, which comprises forming a film of ~400 mg/m 2 and then painting. 2. The surface of the zinc-aluminum alloy plated steel sheet according to claim 1, wherein the chromate aqueous solution contains phosphate ions and the weight ratio of phosphate ions to hexavalent chromium ions is 0.6 to 3. Processing method. 3. Claim 1 characterized in that epoxy resin paint is applied as an undercoat in painting.
A method for surface treatment of a zinc-aluminum alloy plated steel sheet as described in 2.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15801685A JPS6220880A (en) | 1985-07-19 | 1985-07-19 | Surface treatment of zinc-aluminum alloy plated steel sheet |
| AU60084/86A AU6008486A (en) | 1985-07-19 | 1986-07-11 | Alkaline treatment of zinc-aluminium alloys |
| GB8617211A GB2178065B (en) | 1985-07-19 | 1986-07-15 | Process for treatment of zinc-aluminium alloy coatings |
| DE8686109842T DE3679866D1 (en) | 1985-07-19 | 1986-07-17 | METHOD FOR TREATING THE SURFACE OF STEEL SHEET PROVIDED WITH A ZINC / ALUMINUM ALLOY. |
| EP19860109842 EP0209143B1 (en) | 1985-07-19 | 1986-07-17 | Surface treatment process for a sheet iron zinc-aluminium alloy coating |
| DE19863624101 DE3624101A1 (en) | 1985-07-19 | 1986-07-17 | METHOD FOR TREATING THE SURFACE OF STEEL SHEET PROVIDED WITH A ZINC / ALUMINUM ALLOY |
| BR8603404A BR8603404A (en) | 1985-07-19 | 1986-07-18 | PROCESS FOR TREATING THE SURFACE OF A ZINC-ALUMINUM ALLOY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15801685A JPS6220880A (en) | 1985-07-19 | 1985-07-19 | Surface treatment of zinc-aluminum alloy plated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6220880A JPS6220880A (en) | 1987-01-29 |
| JPH0351797B2 true JPH0351797B2 (en) | 1991-08-07 |
Family
ID=15662426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15801685A Granted JPS6220880A (en) | 1985-07-19 | 1985-07-19 | Surface treatment of zinc-aluminum alloy plated steel sheet |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0209143B1 (en) |
| JP (1) | JPS6220880A (en) |
| AU (1) | AU6008486A (en) |
| BR (1) | BR8603404A (en) |
| DE (2) | DE3679866D1 (en) |
| GB (1) | GB2178065B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0235297B1 (en) * | 1985-08-29 | 1992-03-18 | Nisshin Steel Co., Ltd. | Hot-dipped steel plate and process for its production |
| JPH08983B2 (en) * | 1987-03-05 | 1996-01-10 | 新日本製鐵株式会社 | Chromate treatment method with excellent corrosion resistance |
| JPH03226584A (en) * | 1990-01-30 | 1991-10-07 | Nippon Parkerizing Co Ltd | Solution for surface-treating galvanized steel sheet and method therefor |
| JP2697485B2 (en) * | 1992-05-27 | 1998-01-14 | 住友金属工業株式会社 | Manufacturing method of high corrosion resistant galvannealed steel sheet |
| FR2701754B1 (en) * | 1993-02-18 | 1995-04-07 | Pont A Mousson | Pipe element for buried pipe, corresponding buried pipe, and method for protecting such a pipe element. |
| LT3218B (en) | 1993-03-27 | 1995-04-25 | Chemijos Inst | Method for coating zinc alloy by chromium plating |
| JP3983386B2 (en) | 1998-04-03 | 2007-09-26 | 日本ペイント株式会社 | Chromate antirust treatment agent |
| AU2002301945B2 (en) | 2001-11-21 | 2008-07-17 | Chiyoda Chemical Co., Ltd | Surface treatment method of metal member, and metal goods |
| ES2428290T3 (en) * | 2011-03-22 | 2013-11-06 | Henkel Ag & Co. Kgaa | Multi-step anticorrosive treatment for metal components, which at least partially have zinc or zinc alloy surfaces |
| EP2631333A1 (en) * | 2012-02-24 | 2013-08-28 | Henkel AG & Co. KGaA | Pre-treatment of zinc surfaces before passivation |
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| JPS59200768A (en) * | 1983-04-26 | 1984-11-14 | Nippon Paint Co Ltd | Corrosion-resistant composition for treating metallic surface with superior adhesive strength to paint film |
| JPS6126784A (en) * | 1984-07-16 | 1986-02-06 | Nippon Paint Co Ltd | Chemical conversion treated alloy steel sheet plated with zinc containing aluminum |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE316668B (en) * | 1963-09-23 | 1969-10-27 | Parker Ste Continentale | |
| GB1234181A (en) * | 1967-06-14 | 1971-06-03 | ||
| FR1596007A (en) * | 1968-04-18 | 1970-06-15 | ||
| US4227946A (en) * | 1979-02-09 | 1980-10-14 | Oakite Products, Inc. | No-rinse pre-paint coating composition and method |
| FR2560894B1 (en) * | 1984-03-07 | 1988-11-18 | Parker Ste Continentale | PROCESS FOR THE PREPARATION OF ZINC SURFACES, ZINC ALLOYS AND STEEL COATED WITH SUCH MATERIALS FOR RECEIVING PAINTS OR VARNISHES |
| JPS61110777A (en) * | 1984-11-02 | 1986-05-29 | Kawasaki Steel Corp | Surface treating method for preventing black change of galvanizing steel plate |
-
1985
- 1985-07-19 JP JP15801685A patent/JPS6220880A/en active Granted
-
1986
- 1986-07-11 AU AU60084/86A patent/AU6008486A/en not_active Abandoned
- 1986-07-15 GB GB8617211A patent/GB2178065B/en not_active Expired
- 1986-07-17 DE DE8686109842T patent/DE3679866D1/en not_active Expired - Fee Related
- 1986-07-17 DE DE19863624101 patent/DE3624101A1/en not_active Withdrawn
- 1986-07-17 EP EP19860109842 patent/EP0209143B1/en not_active Expired - Lifetime
- 1986-07-18 BR BR8603404A patent/BR8603404A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49135836A (en) * | 1973-05-04 | 1974-12-27 | ||
| JPS5392339A (en) * | 1977-01-25 | 1978-08-14 | Nippon Paint Co Ltd | Metal surface treatment agent |
| JPS5745833A (en) * | 1980-09-01 | 1982-03-16 | Taeko Nakagawa | Stomack camera |
| JPS59200768A (en) * | 1983-04-26 | 1984-11-14 | Nippon Paint Co Ltd | Corrosion-resistant composition for treating metallic surface with superior adhesive strength to paint film |
| JPS6126784A (en) * | 1984-07-16 | 1986-02-06 | Nippon Paint Co Ltd | Chemical conversion treated alloy steel sheet plated with zinc containing aluminum |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6220880A (en) | 1987-01-29 |
| EP0209143B1 (en) | 1991-06-19 |
| EP0209143A2 (en) | 1987-01-21 |
| DE3679866D1 (en) | 1991-07-25 |
| GB8617211D0 (en) | 1986-08-20 |
| EP0209143A3 (en) | 1988-10-26 |
| AU6008486A (en) | 1987-01-22 |
| GB2178065B (en) | 1989-07-19 |
| BR8603404A (en) | 1987-02-24 |
| DE3624101A1 (en) | 1987-01-22 |
| GB2178065A (en) | 1987-02-04 |
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