JPH0153110B2 - - Google Patents
Info
- Publication number
- JPH0153110B2 JPH0153110B2 JP56196749A JP19674981A JPH0153110B2 JP H0153110 B2 JPH0153110 B2 JP H0153110B2 JP 56196749 A JP56196749 A JP 56196749A JP 19674981 A JP19674981 A JP 19674981A JP H0153110 B2 JPH0153110 B2 JP H0153110B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- corrosion resistance
- film
- zinc
- steel sheet
- 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
Links
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 45
- 238000005260 corrosion Methods 0.000 claims description 43
- 230000007797 corrosion Effects 0.000 claims description 43
- 229910000831 Steel Inorganic materials 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000010959 steel Substances 0.000 claims description 33
- 239000003973 paint Substances 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 15
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 13
- 239000008397 galvanized steel Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- -1 silane compound Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002952 polymeric resin Substances 0.000 claims description 5
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 3
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 3
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 65
- 238000011282 treatment Methods 0.000 description 35
- 239000011651 chromium Substances 0.000 description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 21
- 229910052804 chromium Inorganic materials 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000012545 processing Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 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 2
- 238000001879 gelation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- ZPECUSGQPIKHLT-UHFFFAOYSA-N bis(ethenyl)-dimethoxysilane Chemical compound CO[Si](OC)(C=C)C=C ZPECUSGQPIKHLT-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- XZXYTQWKUONLLI-UHFFFAOYSA-N dimethoxy-bis[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound C1OC1COCCC[Si](OC)(OC)CCCOCC1CO1 XZXYTQWKUONLLI-UHFFFAOYSA-N 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
この発明は亜鉛メツキ鋼板、Zn−Fe，Zn−
Ni、或いはZn−Mn，Zn−Al等の合金化亜鉛メ
ツキ鋼板及びアルミニウムメツキ鋼板等、或いは
これらのメツキを多層に形成した複合メツキ鋼板
を素材とする複合被覆板に関し、耐食性及び塗料
密着性、塗装耐食性に優れた性能をもつ鋼板を提
供することを目的とする。
亜鉛メツキ鋼板、合金化亜鉛メツキ鋼板及びア
ルミニウムメツキ鋼板、或いは複合メツキ鋼板の
防錆処理として、従来よりクロメート処理を施し
たものが多く用いられてきている。しかし、その
目的の多くは鋼板製造後から需要化が使用するま
でのいわゆる一次防錆用としてであり、その耐食
性も24〜48時間程度の塩水噴霧試験で白錆が発生
してしまうようなものでしかなかつた。そのため
長期間にわたつて苛酷な腐食環境下におかれる様
な製品では10μ以上の塗装を施すことで腐食を防
止するしかなかつた。しかし近年石油製品の値上
りが激しく、このような塗料を用いずに単に表面
処理を施しただけで優れた耐食性を有する製品の
開発が望まれている。
これに応えるにはクロメート処理によるものが
最適と考えられ、事実塗装型クロメート処理技術
の発展としてクロメート処理液中に各種バインダ
を添加することによつて耐食性能を向上させた製
品が開発されている。しかしこの場合でもその耐
食性は塩水噴霧試験でせいぜい200Hr程度の耐白
錆性しかなく、塗料にかわるべき防食性能を得て
いないのが実情である。
また製品の美観上の問題から塗装が施される場
合でも、塗料のグレードダウンや塗膜厚の軽減に
より塗料のコストダウンを実施する傾向があり、
この場合には高度の耐食性の他に塗料密着性、塗
装耐食性が要求され、これらの性能がバランス良
く満されていることが必要である。
しかしながら、これらの条件をすべて満足する
クロメート処理製品の開発は未だなされておら
ず、高度の耐食性を有していても塗料密着性、塗
装耐食性に難点があるか、或いは逆に塗料密着性
はすぐれていても高度な耐食性は有していない等
の問題があり、完全といえる製品は未だみること
ができない。
これらの例を述べるならば、まず反応型クロメ
ートにより高度の裸耐食性を得ようとするもので
はユニクロム処理として知られるものがある。こ
れはクロム酸及び鉱酸からなる処理液中に長時間
メツキ鋼板を浸漬することにより金属クロム量と
して500〜700mg／m2程度のクロムメート皮膜を形
成させるものである。しかしこのような処理は浸
漬時間が長いこと、処理液の老化が激しいこと等
の欠点があるため、ストリツプコーテイング技術
として用いるには全くそぐわない技術である。ま
たクロメート皮膜が厚いため、割れ易く塗料密着
性に難点が認められる。反対に、クロメート皮膜
を100mg／m2程度に減少させるならば、皮膜割れ
は防げるものの、耐食性は100Hr程度のものにな
り高度の耐食性を有しなくなる。
次に塗布型クロメート処理では、バインダを用
いることによりバインダ中に多量のクロムを固定
し、バインダにより皮膜割れを防ごうとするもの
もあるが、処理液がゲル化しやすかつたり、ゲル
化しない場合でも厚膜であるため乾燥には特別の
方法を必要とする等の欠点がある。
近年これらの欠点を防ぐ目的から、２層処理に
より２層皮膜を形成させたものが提案されてい
る。即ち、まず第１層目に短時間で薄いクロメー
ト皮膜を形成させ、第２層目に無機又は有機物を
塗布して皮膜を形成させ、この第２層皮膜により
第１層のクロメート皮膜を保護しようとするもの
である。無機物を用いるものとしては、特開昭50
−9545号、特公昭53−19981号に示されるように
第１層として電解クロメート皮膜、第２層として
クロム酸及びシリカゾルからなる処理液を塗布、
乾燥して皮膜を形成させたものがある。しかしこ
られは第２層の塗膜層を厚くすることにより高度
の耐食性が得られるものの、厚いシリカ層の皮膜
のため剥離しやすく加工後の耐食性に欠け、また
塗料とシリカゾルとの密着性が悪いため塗装下地
として用いることは困難である。
第２層に有機樹脂を用いた例では特公昭52−
35620号に示されるように第１層にクロム水和酸
化物層を、第２層に水溶性有機樹脂層を形成した
ものがあるが、ここで提案されている有機樹脂層
ではそれ程の効果が望まれない。これは第２層の
有機樹脂中の官能基が水を呼びやすいことから、
高度の耐食性を得ることができないためである。
また第２層を1μ程度に増大させたとしても高度
の耐食性は得られない上、熱風乾燥程度では完全
に皮膜が乾燥しないため特別の装置が必要である
等の問題が認められる。
更に第１層にクロメート皮膜を第２層に有機樹
脂皮膜を形成したものが特公昭49−36100号、特
公昭50−18455号、特公昭49−4611号、特公昭49
−1986号等により提案されている。しかしこれら
はいずれも第２層の有機樹脂中の官能基が水を呼
び易いことから高度の耐食性を得ることは出来な
い。これらはむしろその官能基を利用した塗装下
地としてのみ有効であると考えられる。
以上のように第２層に無機又は有機物を形成し
たものは裸耐食性、塗料密着性のいずれかには効
果があるものの双方を満足し得るものではない。
そこで無機物と有機物とを混合させたものを第２
層として形成させることも考えられるが、この場
合単に混合しているというだけであり逆に単独で
用いた場合の性能を損なう場合が多い。
以上述べたように塗装下地であつてかつ高度の
耐食性を有するクロメート処理鋼板を得ることは
困難であるのが現状である。
本発明はこのような従来技術の現状を打破する
ためになされたもので、亜鉛メツキ鋼板、亜鉛−
鉄、亜鉛−ニツケル、或いは亜鉛−マンガン、亜
鉛−アルミニウム等の合金化亜鉛メツキ鋼板、ア
ルミニウムメツキ鋼板等、更にはこれらのメツキ
を多層に形成した複合メツキ鋼板を素材とし、こ
の表面にいわゆる反応型または塗布型、電解型の
いずれかのクロメート処理を行つてクロメート皮
膜の第１層を形成し、更にその上に所定割合のシ
リカゾルと有機樹脂とをシラン化合物の存在下で
反応結合させた複合有機シリケート樹脂に下記す
る酸素酸及び／又は塩を添加した複合有機シリケ
ート樹脂皮膜の第２層を形成させ、これら第１層
と第２層の相互の効果により優れた塗料密着性、
塗装耐食性及び高度の耐食性を有する鋼板を実現
したものである。このうち第１層、第２層のいず
れが欠けても望まれる性能を得ることができな
い。
素地メツキ鋼板としては、亜鉛メツキ鋼板、亜
鉛−鉄合金化メツキ鋼板、亜鉛−ニツケル合金化
メツキ鋼板、亜鉛−マンガン合金化メツキ鋼板、
亜鉛−アルミニウム合金化メツキ鋼板、アルミニ
ウムメツキ鋼板を用いることができる。また近年
普及しつつある上記メツキを２層以上施した複合
メツキ鋼板であつても良い。亜鉛−鉄合金化メツ
キ鋼板を用いる場合、メツキにおけるFe含有量
は５〜50％、望ましくは10〜30％とする。この範
囲外では耐食性、塗装性が劣化するからである。
また亜鉛−ニツケル合金化メツキ鋼板を用いる場
合、メツキにおけるNi含有量は５〜20％、望ま
しくは12〜13％とする。５％未満では耐食性能が
悪くなり、また20％を超えるとコスト高となり実
用的でないためである。
第１層のクロメート皮膜を形成するクロメート
処理としては、それ自体公知のクロメート処理に
よつても良いが、クロム付着量として10〜150
mg／m2、望ましくは40〜100mg／m2の皮膜を形成
する必要がある。10mg／m2以下では不均一にな
り、150mg／m2以上では溶液の老化とコスト高で
望ましくない。具体的例をあげるならば、まず反
応型クロメート処理液に組成としては、金属クロ
ム換算で１〜100ｇ／の水溶性クロム化合物と、
0.2〜20ｇ／の硫酸から成りかつ全クロム中の
３価クロムの含有量が50％重量以下、好ましくは
20〜35％であることを主成分とするものであつ
て、これに適量の重金属イオン、たとえばZn2+，
Ce2+，Fe3+等の鉱酸たとえばリン酸、弗酸等を
加えても良い。
主成分のうちクロム化合物については金属クロ
ム量に換算して、１ｇ／未満では短時間で所定
のクロメート皮膜を得ることは困難であり、また
100ｇ／をこえると浴安定性を著しく阻害する。
硫酸について言えば、0.2ｇ／未満では短時
間で所定のクロメート皮膜を得ることは難しく、
かつ均一処理性も悪くなる。また20ｇ／以上で
は亜鉛のエツチング速度が早すぎて好ましくな
い。
全クロム量に対するCr3+の割合としては、50％
をこえると浴安定性が悪く、ゲル化しやすくなり
かつ無塗装での耐食性も低下して、所定のクロメ
ート皮膜量があつても高度の耐食性は得られな
い。
この主成分の他に添加し得るZn3+等の重金属
としての役割は、処理液の処理性を向上させるも
のであつて、その添加量は主成分の割合によつて
適当に決めて良い。
次に塗布型クロメート処理液の具体例として
は、上記反応型クロメート処理液中に分子中に多
量のカルボキシル基を含有する水溶性でかつ上記
反応型クロメート処理と相容のある有機高分子樹
脂を添加し、PHを2.0〜3.5に調整したものがあげ
られる。この有機高分子としては、平均分子量
1000〜500000であることが好ましい。その添加量
としては樹脂分に換算して0.02〜30ｇ／の範囲
で選定する。0.02ｇ／未満では皮膜を形成した
際、クロムを完全にその皮膜中にトラツプでき
ず、また30ｇ／を超えると浴の安全性が悪くな
る。PH2.0以下では反応型クロメート処理の性格
が強く、PH3.5以上では浴安定性が損われる。
いずれにしても第１層のクロメート皮膜のクロ
ム量としては10〜150mg／m2あれば良い。但し、
第２層の処理液を塗布した際、第１層からのクロ
ムの溶出があつてはならない。なぜならば、もし
第２層処理時に複合有機シリケート樹脂液中に第
１層から溶出成分が流入すれば樹脂液のバランス
がくずれてしまい、甚しい場合には処理液のゲル
化を招くからである。したがつて第１層処理後、
強制乾燥、水洗等を行い、これにより第１層から
の成分の流出を防ぐことが必要である。
複合有機シリケート樹脂とは、水分散性シリカ
を必須成分とし、これに分子内にヒドロキシル基
を含有する水溶性ないしは水分散性の有機高分子
樹脂（たとえばポリビニルアルコール、ヒドロキ
シエチルセルロース、デンプン、ポリエステル、
アルキツド、エポキシエステル系、アクリル共重
合体等の樹脂）をシラン化合物の存在下で反応結
合させた樹脂の１種または２種以上を混合させた
ものである。ここでいうシリカとは、いわゆるシ
リカゾルであつて粒子径７〜100ｍμ好ましくは
10〜50ｍμのものを使用する。また使用する樹脂
としては、シリカと反応結合すれば、いずれの樹
脂でも良い。更に上記の樹脂骨格中に電子線、紫
外線硬化型の官能基を導入しても良い。
ここで用いたシラン化合物の役割は、上述のシ
リカと有機樹脂との複合化の際、触媒として作用
するとともに、両者の架橋剤及び第１層のクロメ
ート処理皮膜との架橋剤として重要な作用をはた
すもので、それ自体市販のものを用いて良い。
かかるシラン化合物としては、たとえば、ジビ
ニルジメトキシシラン、ジビニルジ−β−メトキ
シエトキシシラン、ジ（γ−グリシドオキシプロ
ピル）ジメトキシシラン、ビニルトリエトキシシ
ラン、ビニルトリス（β−メトキシエトキシノシ
ラン、γ−グリシドオキシプロピルトリメトキシ
シラン、γ−メタクリルオキシプロピルトリメト
キシシラン、β−（３・４−エポキシシクロヘキ
シル）エチルトリメトキシシラン、Ｎ−β（アミ
ノエチル）γ−プロピルメチルジメトキシシラ
ン、Ｎ−β（アミノエチル）γ−アミノプロピル
トリメトキシシラン、γ−アミノプロピルトリエ
トキシシランなどをあげることができる。
シリカ複合体における水分散性シリカと、水溶
性もしくは水分散性の有機樹脂との配合割合は、
固形分の重量百分比で５：95から95：５でなけれ
ばならない。この比率以下では第１層のクロメー
ト皮膜上に塗布しても高度の耐食性は得られず、
またこれ以上では良好な塗料密着性が得られな
い。またシラン化合物の添加量は、シリカ及び有
機樹脂の固形分総重量の0.5〜15％、好ましくは
１〜10％であり、0.5％未満ではクロメート皮膜
との架橋が望まれず、また15％以上ではこの効果
が更に著しく向上することは認められない。
上記複合有機シリケート樹脂処理液にモリブデ
ン、タングステン、バナジウム、錫、ホウ素、ケ
イ素の酸素酸及び／又はこれらの塩を少なくとも
一種以上添加すれば耐食性がより向上することが
見出された。これらの酸素酸及び／又はその塩の
添加量は複合有機シリケート樹脂の固形分換算で
10％以下、好ましくは0.3〜５％の範囲で効果が
ある。これ以上の添加を行つた場合では処理液の
安定性が損われる危険性がある。
このような酸素酸又は塩の加強剤は、経時的な
増粘が比較的少なく、施工性の点で有利である。
更に、紫外線又は電子線硬化型の樹脂を用いる
場合では、酸化亜鉛、アナターゼ型酸化チタン、
チタン酸等の光増感剤に、モリブデン、タングス
テン又はバナジウムからなる酸素酸（たとえば三
酸化バナジウム）、及び／又はその塩（たとえば
オルソバナジン酸リチウム）を用いることによつ
て複合有機シリケート樹脂皮膜の硬化が促進され
る。これは照射により三者の間で酸化還元反応が
起り、樹脂中の官能基と、反応によつて生成した
カチオン性アコ化合物とが塩結合ないしは配位性
結合をおこすためである。その添加量としては一
般に酸素酸またはその塩では固形分換算で樹脂の
0.1〜６％、光増感剤では酸素酸又はその塩の30
〜200％である。
次に第１層のクロメート皮膜と、第２層の複合
有機シリケート樹脂皮膜厚の関係について述べ
る。第１層のクロメート付着量と第２層の膜厚と
の間には図面に示すような相関関係があり、第１
層のクロム付着量10〜150mg／m2に対し、第２層
の皮膜厚さとしては、0.01〜4μが必要である。従
つて所定の耐食性を得るにはこの関係に基づき、
第１層のクロム付着量と第２層の膜厚とを選択す
る必要がある。たとえば500Hrの耐食性を得るに
は、第１層のクロム付着量を40mg／m2とすれば第
２層の膜厚は1.5μ以上、また150mg／m2では0.4μ
以上が必要である。一般的に実用上クロム付着量
10〜150mg／m2に対して第２層の皮膜厚を0.4〜4μ
とするのが望ましい。これは製品の製造上の理由
によるもので、第２層の膜厚を0.4μ以下とした場
合には図面のグラフからわかるようにクロム付着
量の増大が必要とされるため、クロメート処理の
老化が激しく、また4μ以上ではクロメート処理
液の老化に対しては有利であるものの、コスト高
となり通常行われている条件下での溶接が困難と
なるためである。
しかし、それほど高度の耐食性を必要としない
場合には、第１層のクロム付着量10〜150mg／m2
に対し、第２層の膜厚を0.4μ未満0.01μ以上とし
ても良い。この場合望まれる耐食性を与える両層
の条件は図面のグラフを書きかえることにより明
らかになる。すなわち目標とする耐食時間を与え
るクロム付着量と第２層の膜厚とを縦横軸にプロ
ツトしなおせば良い。第２図に耐食時間をパラメ
ータとしたグラフを示す。これによれば、たとえ
ば200Hrの耐食性を与えるには、第２層の膜厚
0.1μに対して第１層のクロム付着量80mg／m2、
0.02μに対して120mg／m2とすれば良いことがわか
る。
第１層の付着量と第２層の皮膜厚との関係は上
記の通りであるが、いずれにしてもクロメート皮
膜及び複合有機シリケート皮膜の２層構造をとる
ことが必要であり、このような２層構造としない
場合には高度の耐食性を得ることは出来ない。
次に実施例を示す。
第１表に示すような種々の異なる第１層のクロ
メート付着量と第２層の膜厚とを有する本発明鋼
板No.１〜No.22につき塩水噴霧試験での白錆発生と
塗料密着性および塗装耐食性試験を行つた。ま
た、第２表に示す比較鋼板No.23〜No.40についても
同様の試験を行つた。
なお、第１層のクロメート処理液としては、
Ａ：（CrO3，H2SO4，H3PO4）＝10ｇ／，２
ｇ／，２ｇ／）
Ｂ：（CrO3，H2SO4，Cr3+，Zn2+）＝（10ｇ／，
２ｇ／，２ｇ／，３ｇ／）
Ｃ：Ｂに分子量約10万のポリアクリル酸を２ｇ／
添加、アンモニア水によりPHを３に調整し
たもの
の３種を代表として使用した。
また複合有機シリケート処理液としては、有機
樹脂としてアクリル共重合体とエポキシ樹脂とが
70：30の比の混合物に対してシリカゾルを60：40
の比になるようにγ−メタクリルオキシプロピル
トリメトキシシラン1.5wt％（有機樹脂とシリカ
ゾルの固形分総重量に対して）の存在下で反応結
合したものを使用した。但し処理液がこれらのも
のに限定されないことは云うまでもない。
素材としては片面10ｇ／m2の亜鉛付着量を有す
る電気亜鉛メツキ鋼板、亜鉛−ニツケル合金化メ
ツキ鋼板、電気メツキによる亜鉛−鉄合金化メツ
キ鋼板を使用した。これは他の合金化亜鉛メツキ
鋼板又はアルミニウムメツキ鋼板であつても良
い。
処理工程は下記に従つた。
弱アルカリ脱脂→水洗→絞り→反応型クロメー
ト処理（Ａ，Ｂ）→絞り→水洗→乾燥→複合有機
シリケート塗布→乾燥。
弱アルカリ脱脂→水洗→絞り→塗布型クロメー
ト処理（Ｃ）→強制乾燥→複合有機シリケート塗
布→乾燥。
なお、塗料密着性は以下のようにして評価し
た。
塗料密着性評価基準
◎……加工後のテープ剥離による剥離が全く認
められない。
〇……加工後のテープ剥離による剥離がごく若
干認められる。
△……加工後のテープ剥離による剥離が約40％
認められる。
×……加工後のテープ剥離による剥離が約40％
以上認められる。
第１表および第２表から本発明鋼板が比較鋼板
に較べて格段の耐食性を有していることが判る。
また塗装密着性においても、従来のリン酸塩処理
（比較鋼No.31）と比較して優れていることが示さ
れている。なお、比較鋼No.24は複合有機シリケー
ト樹脂に対するメタバナジン酸アンモニウムの添
加量が10％を超えた例であり、この比較例では処
理液の安定性が低下する現象がみられた。
This invention relates to galvanized steel sheets, Zn-Fe, Zn-
Composite coated plates made of Ni, Zn-Mn, Zn-Al alloyed galvanized steel sheets, aluminum plated steel sheets, etc., or composite plated steel sheets formed with multiple layers of these platings, have corrosion resistance, paint adhesion, The objective is to provide a steel plate with excellent paint corrosion resistance. Conventionally, chromate treatment has been widely used as a rust preventive treatment for galvanized steel sheets, alloyed galvanized steel sheets, aluminum-plated steel sheets, or composite galvanized steel sheets. However, most of its purpose is for so-called primary rust prevention from the time the steel plate is manufactured until it is used in demand, and its corrosion resistance is such that white rust occurs during a salt spray test for about 24 to 48 hours. It was all I could do. Therefore, for products that are exposed to harsh corrosive environments for long periods of time, the only way to prevent corrosion is to apply a coating with a thickness of 10μ or more. However, in recent years, the price of petroleum products has increased sharply, and there is a desire to develop products that have excellent corrosion resistance simply by surface treatment without using such paints. Chromate treatment is thought to be the best way to meet this demand, and in fact, as a development of paint-type chromate treatment technology, products with improved corrosion resistance have been developed by adding various binders to the chromate treatment solution. . However, even in this case, the corrosion resistance is only white rust resistance of about 200 hours at most in a salt spray test, and the reality is that it does not have the anticorrosion performance that should replace paint. Furthermore, even when painting is applied due to aesthetic issues, there is a tendency to reduce the cost of paint by downgrading the paint or reducing the thickness of the paint film.
In this case, in addition to high corrosion resistance, paint adhesion and paint corrosion resistance are required, and it is necessary that these performances are satisfied in a well-balanced manner. However, a chromate-treated product that satisfies all of these conditions has not yet been developed, and even if it has a high degree of corrosion resistance, it has problems with paint adhesion and paint corrosion resistance, or conversely, it has excellent paint adhesion. However, there are problems such as not having a high degree of corrosion resistance, and there are still no products that can be considered perfect. To describe these examples, first, there is a process known as Unichrome treatment, which attempts to obtain a high degree of bare corrosion resistance using reactive chromates. This method forms a chromate film with a metallic chromium content of about 500 to 700 mg/m 2 by immersing a galvanized steel sheet in a treatment solution consisting of chromic acid and mineral acid for a long time. However, this type of treatment has drawbacks such as a long immersion time and severe aging of the treatment solution, making it completely unsuitable for use as a strip coating technique. Also, because the chromate film is thick, it is easily broken and has problems with paint adhesion. On the other hand, if the chromate film is reduced to about 100 mg/m 2 , film cracking can be prevented, but the corrosion resistance will be only about 100 hours, meaning that it will no longer have a high degree of corrosion resistance. Next, some coating-type chromate treatments use a binder to fix a large amount of chromium in the binder to prevent film cracking, but in some cases the treatment solution tends to gel or does not gel. However, since it is a thick film, it has drawbacks such as requiring a special method for drying. In recent years, in order to prevent these drawbacks, a two-layer film formed by two-layer treatment has been proposed. That is, first, a thin chromate film is formed on the first layer in a short period of time, then an inorganic or organic substance is applied to the second layer to form a film, and this second layer film protects the first chromate film. That is. For those using inorganic substances, there is
As shown in Japanese Patent Publication No. 53-19981, an electrolytic chromate film is applied as the first layer, and a treatment solution consisting of chromic acid and silica sol is applied as the second layer.
Some are dried to form a film. However, although a high degree of corrosion resistance can be obtained by increasing the thickness of the second coating layer, the thick silica layer easily peels off and lacks corrosion resistance after processing, and the adhesion between the paint and silica sol is poor. Due to its poor quality, it is difficult to use it as a base for painting. In an example using an organic resin for the second layer,
As shown in No. 35620, there is a method in which a chromium hydrated oxide layer is formed as the first layer and a water-soluble organic resin layer is formed as the second layer, but the organic resin layer proposed here does not have such an effect. Not wanted. This is because the functional groups in the organic resin of the second layer easily attract water.
This is because a high degree of corrosion resistance cannot be obtained.
Further, even if the second layer is increased to about 1μ, a high degree of corrosion resistance cannot be obtained, and there are problems such as the need for special equipment because the film is not completely dried by hot air drying. In addition, the first layer is a chromate film and the second layer is an organic resin film.
- Proposed by No. 1986, etc. However, none of these can provide a high degree of corrosion resistance because the functional groups in the organic resin of the second layer tend to attract water. Rather, these are considered to be effective only as paint bases that utilize their functional groups. As described above, the second layer formed with an inorganic or organic substance is effective in either bare corrosion resistance or paint adhesion, but cannot satisfy both.
Therefore, a mixture of inorganic and organic substances is used as a second
Although it is possible to form them as a layer, in this case they are merely mixed, and on the contrary, the performance when used alone is often impaired. As described above, it is currently difficult to obtain a chromate-treated steel sheet that is a coating base and has a high degree of corrosion resistance. The present invention has been made to overcome the current state of the prior art, and is based on galvanized steel sheets and zinc-plated steel sheets.
The material is alloyed galvanized steel sheets such as iron, zinc-nickel, zinc-manganese, zinc-aluminum, etc., aluminum-plated steel sheets, etc., and composite plated steel sheets with multilayers of these platings. Alternatively, the first layer of the chromate film is formed by coating-type or electrolytic chromate treatment, and then a composite organic film is formed by reacting and bonding a predetermined ratio of silica sol and organic resin in the presence of a silane compound. A second layer of a composite organic silicate resin film is formed by adding the following oxygen acid and/or salt to a silicate resin, and the mutual effects of these first and second layers provide excellent paint adhesion.
This is a steel plate that has painted corrosion resistance and a high degree of corrosion resistance. If either the first layer or the second layer is missing, desired performance cannot be obtained. The base plated steel sheets include galvanized steel sheets, zinc-iron alloyed plated steel sheets, zinc-nickel alloyed plated steel sheets, zinc-manganese alloyed plated steel sheets,
A zinc-aluminum alloy plated steel plate or an aluminum plated steel plate can be used. Alternatively, it may be a composite plated steel sheet having two or more layers of the above-mentioned plating, which has become popular in recent years. When using a zinc-iron alloy plated steel sheet, the Fe content in the plate is 5 to 50%, preferably 10 to 30%. This is because corrosion resistance and paintability deteriorate outside this range.
Further, when using a zinc-nickel alloy plated steel sheet, the Ni content in the plate is 5 to 20%, preferably 12 to 13%. This is because if it is less than 5%, the corrosion resistance performance will deteriorate, and if it exceeds 20%, the cost will be high and it is not practical. The chromate treatment to form the first layer chromate film may be a chromate treatment known per se, but the amount of chromium deposited is 10 to 150.
It is necessary to form a film of mg/m 2 , preferably 40 to 100 mg/m 2 . If it is less than 10 mg/m 2 , it will become non-uniform, and if it is more than 150 mg/m 2 , it will cause aging of the solution and increase the cost, which is not desirable. To give a specific example, first, the composition of the reactive chromate treatment solution is 1 to 100 g/water-soluble chromium compound in terms of metallic chromium,
It consists of 0.2 to 20 g of sulfuric acid and the content of trivalent chromium in the total chromium is 50% by weight or less, preferably
The main component is 20 to 35%, and an appropriate amount of heavy metal ions, such as Zn 2+ ,
Mineral acids such as Ce 2+ and Fe 3+ , such as phosphoric acid and hydrofluoric acid, may be added. Among the main components, it is difficult to obtain a desired chromate film in a short time when the amount of chromium compounds is less than 1 g/metal chromium.
If it exceeds 100g/, bath stability will be significantly impaired. Regarding sulfuric acid, it is difficult to obtain the desired chromate film in a short time with less than 0.2g/
In addition, uniform processability also deteriorates. Further, if the amount is 20 g or more, the etching rate of zinc is too fast, which is not preferable. The ratio of Cr 3+ to the total amount of chromium is 50%
If the chromate coating exceeds this amount, the bath stability will be poor, gelation will occur easily, and the corrosion resistance without coating will also decrease, making it impossible to obtain a high degree of corrosion resistance even with a predetermined amount of chromate film. The role of heavy metals such as Zn 3+ , which can be added in addition to the main components, is to improve the processability of the processing solution, and the amount added may be appropriately determined depending on the ratio of the main components. Next, as a specific example of the coating-type chromate treatment liquid, an organic polymer resin that is water-soluble and has a large amount of carboxyl groups in its molecules and is compatible with the above-mentioned reactive chromate treatment is added to the above-mentioned reactive chromate treatment liquid. Examples include those in which the pH is adjusted to 2.0 to 3.5. This organic polymer has an average molecular weight of
It is preferably 1000 to 500000. The amount added is selected in the range of 0.02 to 30 g/resin content. If it is less than 0.02 g/l, chromium cannot be completely trapped in the film when it is formed, and if it exceeds 30 g/l, the safety of the bath will deteriorate. At pH 2.0 or lower, the character of reactive chromate treatment is strong, and at pH 3.5 or higher, bath stability is impaired. In any case, the amount of chromium in the first layer chromate film may be 10 to 150 mg/ m2 . however,
When the second layer treatment liquid is applied, chromium must not be leached from the first layer. This is because, if eluted components from the first layer flow into the composite organic silicate resin solution during second layer processing, the balance of the resin solution will be disrupted, and in severe cases, it will cause gelation of the processing solution. . Therefore, after the first layer treatment,
It is necessary to perform forced drying, washing with water, etc. to prevent components from flowing out from the first layer. Composite organic silicate resin has water-dispersible silica as an essential component, and contains water-soluble or water-dispersible organic polymer resins containing hydroxyl groups in the molecule (e.g., polyvinyl alcohol, hydroxyethyl cellulose, starch, polyester, etc.).
It is a mixture of one or more resins in which resins such as alkyd, epoxy ester, and acrylic copolymers are reacted and bonded in the presence of a silane compound. The silica referred to here is a so-called silica sol, and preferably has a particle size of 7 to 100 mμ.
Use one with a diameter of 10 to 50 mμ. Further, as the resin used, any resin may be used as long as it is reactively bonded to silica. Furthermore, electron beam or ultraviolet ray curing functional groups may be introduced into the resin skeleton. The role of the silane compound used here is to act as a catalyst when the above-mentioned silica and organic resin are combined, and also to play an important role as a crosslinking agent for both and the chromate treatment film of the first layer. A commercially available product may be used. Examples of such silane compounds include divinyldimethoxysilane, divinyldi-β-methoxyethoxysilane, di(γ-glycidoxypropyl)dimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxynosilane, γ-glycidoxysilane) Propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β(aminoethyl)γ-propylmethyldimethoxysilane, N-β(aminoethyl) Examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The blending ratio of water-dispersible silica and water-soluble or water-dispersible organic resin in the silica composite is as follows:
The weight percentage of solids should be between 5:95 and 95:5. If the ratio is below this level, high corrosion resistance cannot be obtained even if the coating is applied on the first layer of chromate film.
Moreover, if it is more than this, good paint adhesion cannot be obtained. The amount of the silane compound added is 0.5 to 15%, preferably 1 to 10%, based on the total solid weight of silica and organic resin. If it is less than 0.5%, crosslinking with the chromate film is not desired, and if it is more than 15%, No significant improvement in this effect was observed. It has been found that corrosion resistance can be further improved by adding at least one of molybdenum, tungsten, vanadium, tin, boron, and silicon oxygen acids and/or salts thereof to the composite organic silicate resin treatment solution. The amount of these oxygen acids and/or their salts added is based on the solid content of the composite organic silicate resin.
It is effective at a content of 10% or less, preferably in the range of 0.3 to 5%. If more than this is added, there is a risk that the stability of the treatment liquid will be impaired. Such oxyacid or salt toughening agents have relatively little increase in viscosity over time and are advantageous in terms of workability. Furthermore, when using an ultraviolet or electron beam curing resin, zinc oxide, anatase titanium oxide,
The composite organic silicate resin film can be improved by using an oxyacid made of molybdenum, tungsten or vanadium (e.g. vanadium trioxide) and/or a salt thereof (e.g. lithium orthovanadate) as a photosensitizer such as titanic acid. Hardening is accelerated. This is because irradiation causes a redox reaction between the three, and a salt bond or coordinate bond is formed between the functional group in the resin and the cationic aco compound produced by the reaction. Generally speaking, the amount of oxygen acid or its salt added is based on the solid content of the resin.
0.1-6%, 30% of oxygen acid or its salt in photosensitizer
~200%. Next, the relationship between the thickness of the first layer chromate film and the second layer composite organic silicate resin film will be described. There is a correlation between the amount of chromate deposited in the first layer and the thickness of the second layer, as shown in the drawing.
For a chromium deposition amount of the layer of 10 to 150 mg/m 2 , the film thickness of the second layer is required to be 0.01 to 4 μm. Therefore, based on this relationship, to obtain the specified corrosion resistance,
It is necessary to select the amount of chromium deposited in the first layer and the thickness of the second layer. For example, to obtain corrosion resistance of 500 hours, if the amount of chromium deposited in the first layer is 40mg/ m2 , the thickness of the second layer is 1.5μ or more, and at 150mg/ m2 , the thickness of the second layer is 0.4μ.
The above is necessary. Generally, the amount of chromium deposited in practical use
The thickness of the second layer is 0.4-4μ for 10-150mg/ m2 .
It is desirable to do so. This is due to product manufacturing reasons.If the thickness of the second layer is set to 0.4μ or less, as can be seen from the graph in the drawing, an increase in the amount of chromium deposited is required. This is because, although it is advantageous for aging of the chromate treatment solution when the chromate treatment liquid is more than 4μ, it increases the cost and makes it difficult to weld under normal conditions. However, if a very high degree of corrosion resistance is not required, the amount of chromium deposited in the first layer should be 10 to 150 mg/ m2.
On the other hand, the thickness of the second layer may be less than 0.4μ and 0.01μ or more. In this case, the conditions for both layers that provide the desired corrosion resistance will become clear by redrawing the graphs in the drawings. That is, the amount of chromium deposited and the film thickness of the second layer that provide the target corrosion resistance time can be plotted on the vertical and horizontal axes. Figure 2 shows a graph using corrosion resistance time as a parameter. According to this, for example, in order to provide corrosion resistance of 200 hours, the thickness of the second layer must be
The amount of chromium deposited in the first layer is 80mg/m 2 for 0.1μ,
It can be seen that 120mg/m 2 is sufficient for 0.02μ. The relationship between the deposition amount of the first layer and the film thickness of the second layer is as described above, but in any case, it is necessary to have a two-layer structure of a chromate film and a composite organic silicate film, and such If it does not have a two-layer structure, a high degree of corrosion resistance cannot be obtained. Next, examples will be shown. White rust occurrence and paint adhesion in the salt spray test for the steel sheets No. 1 to No. 22 of the present invention having various first layer chromate adhesion amounts and second layer film thicknesses as shown in Table 1. And a paint corrosion resistance test was conducted. Similar tests were also conducted on comparative steel plates No. 23 to No. 40 shown in Table 2. The chromate treatment liquid for the first layer is A: (CrO 3 , H 2 SO 4 , H 3 PO 4 )=10 g/,2
g/, 2g/) B: (CrO 3 , H 2 SO 4 , Cr 3+ , Zn 2+ ) = (10g/,
2g/, 2g/, 3g/) C: Add 2g/ of polyacrylic acid with a molecular weight of approximately 100,000 to B.
Three types were used as representatives, the pH of which was adjusted to 3 with addition of ammonia water. In addition, the composite organic silicate treatment liquid uses an acrylic copolymer and an epoxy resin as organic resins.
60:40 silica sol to 70:30 ratio mixture
γ-methacryloxypropyltrimethoxysilane was reacted and bonded in the presence of 1.5 wt% (based on the total solid weight of the organic resin and silica sol) so that the ratio was as follows. However, it goes without saying that the processing liquid is not limited to these. The materials used were an electrogalvanized steel sheet with a zinc coating amount of 10 g/m 2 on one side, a zinc-nickel alloyed steel sheet, and an electroplated zinc-iron alloyed steel sheet. This may also be other alloyed galvanized steel or aluminized steel. The processing steps were as follows. Weak alkaline degreasing → water washing → squeezing → reactive chromate treatment (A, B) → squeezing → water washing → drying → complex organic silicate application → drying. Weak alkaline degreasing → water washing → squeezing → coated chromate treatment (C) → forced drying → complex organic silicate coating → drying. In addition, paint adhesion was evaluated as follows. Paint adhesion evaluation criteria ◎...No peeling due to tape peeling after processing is observed. 〇...Very slight peeling due to tape peeling after processing is observed. △……Approximately 40% peeling due to tape peeling after processing
Is recognized. ×……Approximately 40% peeling due to tape peeling after processing
The above is recognized. It can be seen from Tables 1 and 2 that the steel sheets of the present invention have significantly higher corrosion resistance than the comparative steel sheets.
It has also been shown that paint adhesion is superior to conventional phosphate treatment (comparative steel No. 31). In addition, comparative steel No. 24 is an example in which the amount of ammonium metavanadate added to the composite organic silicate resin exceeds 10%, and a phenomenon in which the stability of the treatment liquid decreased was observed in this comparative example.
【表】
＊ 原板たるメツキ鋼板は、 いずれも電気メツキ
鋼板
[Table] * The plated steel sheets that are the base plates are all electroplated steel sheets.
【表】【table】
【表】
注
１ メラミンアルキツド系塗料（塗膜厚30μ）
２ １mm四方のマス目がタテ、ヨコ10ケずつ
３ 注）２）を実施後５mm押出し、
４ 1/2φのポンチにて、１Kgのおもりを50cmの
高さから落下
５ JIS―Ｚ―2371の塩水噴霧試験法による
６ 注）１）の塗料を使用、クロスカツトを入
れ、注）５）の方法によりSSTに360Hrかけ、
テープ剥離。[Table] Note 1 Melamine alkyd paint (film thickness 30μ) 2 1 mm square squares 10 vertically and horizontally 3 Note) After performing 2), extrude 5 mm and use a 4 1/2φ punch to weigh 1 kg. Drop a weight from a height of 50 cm 5 Based on the salt spray test method of JIS-Z-2371 6 Note) Use the paint in 1), insert a cross cut, apply SST for 360 hours using the method in Note) 5),
Tape removal.
第１図及び第２図は亜鉛メツキ鋼板に本発明に
よる処理を施した例であつて、第１層のクロメー
ト処理液としてはＡを使用し、そのクロム付着量
及び第２層膜厚と耐食性との関係を示すグラフで
ある。
Figures 1 and 2 show examples of galvanized steel sheets treated according to the present invention, in which A was used as the chromate treatment solution for the first layer, and the amount of chromium deposited, the thickness of the second layer, and the corrosion resistance. It is a graph showing the relationship between
Claims (1)
ル、亜鉛−マンガン、亜鉛−アルミニウム等の合
金化亜鉛メツキ鋼板、又はアルミニウムメツキ鋼
板、若しくはこれらメツキを多層に形成した複合
メツキ鋼板等の表面にクロメート被膜を10〜150
mg／m2の付着量で形成し、該クロメート皮膜の上
に、下記割合のシリカゾルと分子内にヒドロキシ
ル基を含有する水溶性又は水分散性の有機高分子
樹脂を下記量のシラン化合物の存在下で反応結合
させた複合有機シリケート樹脂に、モリブデン、
タングステン、バナジウム、錫、ホウ素又はケイ
素の酸素酸及び／又はその塩のうちの１種又は２
種以上を複合有機シリケート樹脂の固形分重量の
10％以下の範囲で添加した複合有機シリケート樹
脂皮膜を0.01〜4μの膜厚で形成したことを特徴と
する耐食性、塗料密着性、塗装耐食性の優れた複
合被覆鋼板。 シリカゾルと有機高分子樹脂の固形分重量百分
比：５：95〜95：５ シラン化合物：シリカゾル及び有機高分子樹脂
の固形分総重量の0.5〜15wt％[Scope of Claims] 1. Galvanized steel sheet, alloyed galvanized steel sheet such as zinc-iron, zinc-nickel, zinc-manganese, zinc-aluminum, etc., or aluminum-plated steel sheet, or a composite plated steel sheet in which these platings are formed in multiple layers. 10~150 chromate film on the surface of etc.
mg/ m2 , and on the chromate film, silica sol in the following ratio and water-soluble or water-dispersible organic polymer resin containing hydroxyl groups in the molecule are added in the presence of the following amount of silane compound. Molybdenum,
One or two of tungsten, vanadium, tin, boron or silicon oxygen acids and/or salts thereof
The solid content of the composite organic silicate resin is
A composite coated steel sheet with excellent corrosion resistance, paint adhesion, and paint corrosion resistance, characterized by forming a composite organic silicate resin film with a film thickness of 0.01 to 4 μm with addition of 10% or less. Solid weight percentage of silica sol and organic polymer resin: 5:95-95:5 Silane compound: 0.5-15 wt% of the total solid weight of silica sol and organic polymer resin
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19674981A JPS5898172A (en) | 1981-12-09 | 1981-12-09 | Compound coated steel sheet excellent in corrosion resistance, paint adhesiveness of steel sheet and corrosion resistance of coating |
| DE19813151115 DE3151115A1 (en) | 1980-12-24 | 1981-12-23 | Surface-coated strip steel of good corrosion resistance, paintability and corrosion resistance after application of paint |
| CA000393175A CA1211406A (en) | 1980-12-24 | 1981-12-23 | Plated steel sheet with chromate and composite silicate resin films |
| AU79122/81A AU547534B2 (en) | 1980-12-24 | 1981-12-24 | Plated steel sheets coated with chromate and then a silicate resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19674981A JPS5898172A (en) | 1981-12-09 | 1981-12-09 | Compound coated steel sheet excellent in corrosion resistance, paint adhesiveness of steel sheet and corrosion resistance of coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5898172A JPS5898172A (en) | 1983-06-10 |
| JPH0153110B2 true JPH0153110B2 (en) | 1989-11-13 |
Family
ID=16362963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19674981A Granted JPS5898172A (en) | 1980-12-24 | 1981-12-09 | Compound coated steel sheet excellent in corrosion resistance, paint adhesiveness of steel sheet and corrosion resistance of coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5898172A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02104673A (en) * | 1988-10-13 | 1990-04-17 | Sumitomo Metal Ind Ltd | Chromated galvanized steel material having light color tone |
| JPH07106611B2 (en) * | 1990-03-20 | 1995-11-15 | 川崎製鉄株式会社 | Method for producing organic composite coated steel sheet having excellent corrosion resistance and weldability |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53121034A (en) * | 1977-03-31 | 1978-10-23 | Kansai Paint Co Ltd | Surface treatment of metal |
| JPS53123435A (en) * | 1977-04-04 | 1978-10-27 | Kansai Paint Co Ltd | Method of treating metal surface |
-
1981
- 1981-12-09 JP JP19674981A patent/JPS5898172A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53121034A (en) * | 1977-03-31 | 1978-10-23 | Kansai Paint Co Ltd | Surface treatment of metal |
| JPS53123435A (en) * | 1977-04-04 | 1978-10-27 | Kansai Paint Co Ltd | Method of treating metal surface |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5898172A (en) | 1983-06-10 |
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