JP4550956B2 - Painted metal plate with excellent anticorrosion paint and corrosion resistance - Google Patents
Painted metal plate with excellent anticorrosion paint and corrosion resistance Download PDFInfo
- Publication number
- JP4550956B2 JP4550956B2 JP22651299A JP22651299A JP4550956B2 JP 4550956 B2 JP4550956 B2 JP 4550956B2 JP 22651299 A JP22651299 A JP 22651299A JP 22651299 A JP22651299 A JP 22651299A JP 4550956 B2 JP4550956 B2 JP 4550956B2
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- Prior art keywords
- corrosion resistance
- metal plate
- treatment
- paint
- resin
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- 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.)
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- 239000003973 paint Substances 0.000 title claims description 36
- 229910052751 metal Inorganic materials 0.000 title claims description 32
- 239000002184 metal Substances 0.000 title claims description 32
- 230000007797 corrosion Effects 0.000 title claims description 29
- 238000005260 corrosion Methods 0.000 title claims description 29
- 238000011282 treatment Methods 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- 230000003449 preventive effect Effects 0.000 claims description 13
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 3
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
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- 229910000831 Steel Inorganic materials 0.000 description 36
- 239000010959 steel Substances 0.000 description 36
- 239000000049 pigment Substances 0.000 description 32
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 description 9
- 239000008397 galvanized steel Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
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- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
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- 230000008961 swelling Effects 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- REEFSLKDEDEWAO-UHFFFAOYSA-N Chloraniformethan Chemical compound ClC1=CC=C(NC(NC=O)C(Cl)(Cl)Cl)C=C1Cl REEFSLKDEDEWAO-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 2
- 239000000999 acridine dye Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
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- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
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- 239000001007 phthalocyanine dye Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
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- XEFUJGURFLOFAN-UHFFFAOYSA-N 1,3-dichloro-5-isocyanatobenzene Chemical compound ClC1=CC(Cl)=CC(N=C=O)=C1 XEFUJGURFLOFAN-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は塗装鋼板に関する。さらに詳しくは、耐食性に優れ、有毒とされるクロムを含まないため毒性が低く、建材用や家電用として好適な塗装金属板に関するものである。
【０００２】
【従来の技術】
家電や建材などの分野で切断・加工後に塗装をするポスト塗装鋼板に代わって、プレコート鋼板と呼ばれる切断・加工前に塗装を施した製品の使用量が増えてきている。これは鉄鋼メーカーが塗装を行うプレコート鋼板を使用することにより、家電メーカーなどでは塗装ラインを持つ必要が無くなることや、ポストコート鋼板よりプレコート鋼板の方が平滑で美しい外観を持つからである。
【０００３】
一般にプレコート鋼板のような塗装鋼板に厳しい加工を施すと塗装がダメージを受けて耐食性が低下することが知られている。また、プレコート鋼板を切断すると裸の鋼板が露出するため、その部分で腐食が発生する懸念がある。つまり、プレコート鋼板は優れた耐食性を有する必要がある。
このようなプレコート鋼板の耐食性を改善した例として、例えば、特開平８−１６８７２３号公報には、皮膜の構造を規定することによって加工性と耐汚染性、硬度に優れたプレコート鋼板を得る技術が開示されている。また、特開平３−１００１８０号公報には、特定のクロメート処理液を用いることで端面耐食性を改善したプレコート鋼板が開示されている。
【０００４】
いずれにおいても、耐食性に優れるめっき鋼板の上にクロメート処理と呼ばれる耐食性と密着性に優れる下地処理を施し、その上に耐食性に優れるクロム系防錆顔料を含む下塗り層を有し、さらにその上に着色された上塗り層を有する構造をとっている。
【０００５】
【発明が解決しようとする課題】
これらクロメート処理およびクロム系防錆顔料に含まれる６価のクロムは水溶性であり、これが溶出することによって亜鉛系のめっき鋼板の腐食を抑制する性質がある。例えば、厳しい加工で塗膜が割れた場合や切断部で裸の鋼板が露出した場合でも、その部分の腐食を抑制するなど、非常に優れており、今日までクロメート処理とクロム系防錆顔料は幅広くプレコート鋼板に使用されてきている。
【０００６】
しかしながら、クロメート処理およびクロム系防錆顔料から溶出する可能性のある６価のクロムの毒性から、最近ではクロムフリーの下地処理、クロムフリーの防錆顔料に対する要望が高まっている。
そこで、本発明では、このような要望に答え、耐食性に優れるクロムフリーの低毒性の防食塗料とその塗料を処理した塗装金属板を提供する事を目的とする。
【０００７】
【課題を解決するための手段】
本発明者らは、各種めっき鋼板の切断端面部の耐食性を各種クロムフリー下地処理と各種クロムフリープライマーの条件で様々な検討を重ねた。その結果、防錆塗料としてクロム系防錆顔料の代わりにリン酸を含有する塗料を使用して塗装する事により、優れた端面部の耐食性を有する低毒性のクロムフリープレコート金属板を製造しうることを見いだして本発明に至った。
【０００８】
すなわち、本発明の趣旨とするところは、以下のとおりである。
（１）金属板の少なくとも片面に、防錆添加剤として、ピロリン酸、次リン酸、亜リン酸、次亜リン酸の１種もしくは２種以上を、合計で０．１ｗｔ％以上４０ｗｔ％未満含有する防食塗料からなり、乾燥膜厚が０．２μｍ以上１００μｍ未満である塗膜を有し、該塗膜の下地処理としてリン酸亜鉛処理、シランカップリング処理、複合酸化被膜処理、タンニン酸処理、これらの混合処理のいずれかが施されていることを特徴とする耐食性に優れる塗装金属板。
【０００９】
（２）防食塗料からなる塗膜の上層に、着色された塗膜を、さらに有することを特徴とする前記（１）に記載の耐食性に優れる塗装金属板。
【００１０】
【発明の実施の形態】
以降、本発明のピロリン酸、次リン酸、亜リン酸、次亜リン酸を総称してリンの酸素酸と呼ぶことにする。
【００１１】
本発明のリンの酸素酸は市販のものを特別な前処理を行うことなく使用することが可能である。本発明のリンの酸素酸を防錆添加剤として用いることにより塗装金属板の耐食性が向上するメカニズムは明確になっていないが、以下のように推定される。すなわち、本発明の塗装金属板の切断端面部が腐食しやすい環境、すなわち濡れ環境に置かれた時にリン酸イオンが溶出し、このリン酸イオンが端面部の裸の金属と反応して安定なリン酸塩を形成することが耐食性の向上に寄与しているものと推定される。
【００１２】
本発明の防食塗料に添加されるリンの酸素酸の添加量は、単独に添加する場合でも、２種以上を混合して添加する場合でも０．１ｗｔ％以上である。０．１ｗｔ％未満では添加したことによる耐食性の向上効果が認められない。上限については特に設定しないが、４０ｗｔ％を越えると成膜が困難になるので、４０ｗｔ％未満とする。
【００１３】
本発明の防食塗料はリンの酸素酸と成膜可能な樹脂を含むことを特徴とする。
本発明の防錆塗料に用いられる樹脂としては用途に応じて一般に公知の樹脂を適用することができる。すなわち、ポリオレフィン樹脂、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、塩化ビニル樹脂、フッ素系樹脂、ブチラール樹脂、ポリカーボネート樹脂、フェノール樹脂などである。これらの混合物や共重合物も使用できる。また、これらにイソシアネート樹脂、アミノ樹脂、シランカップリング剤あるいはチタンカップリング剤等を補助成分として併用することができる。
【００１４】
本発明によるプレコート金属板は加工後に補修をされずにそのまま使用されるケースが多いので、厳しい加工が施される用途では、ポリエステル樹脂をメラミンで架橋する樹脂系、ポリエステル樹脂をウレタン樹脂（イソシアネート、イソシアネート樹脂）で架橋する樹脂系、塩化ビニル樹脂系、フッ素樹脂系（溶剤可溶型、アクリル樹脂との分散混合型）が望ましい。
【００１５】
塗料としての形態は特に限定するものではなく、有機溶剤系塗料、水系塗料、コロイド分散系塗料、粉体塗料、電着塗料などが挙げられる。
本発明の防錆塗料は必要に応じて他の防錆顔料を含んでもよい。防錆顔料としては、例えば、▲１▼リン酸亜鉛、リン酸鉄、リン酸アルミニウム、亜リン酸亜鉛、等のリン酸系防錆顔料、▲２▼モリブデン酸カルシウム、モリブデン酸アルミニウム、モリブデン酸バリウム、等のモリブデン酸系防錆顔料、▲３▼酸化バナジウムなどのバナジウム系防錆顔料、▲４▼カルシウムシリケートなどのシリケート系顔料、▲５▼ストロンチウムクロメート、ジンククロメート、カルシウムクロメート、カリウムクロメート、バリウムクロメートなどのクロメート系防錆顔料、▲６▼水分散シリカ、ヒュームドシリカ、等の微粒シリカなどを用いることができる。しかし▲５▼のクロメート系防錆顔料は環境上有毒であるため、これら以外を使用することが望ましい。
【００１６】
本発明の防錆塗料は必要に応じて着色をしてもよい。着色は一般的な顔料や染料などによる。顔料としては、無機系、有機系、両者の複合系に関わらず公知のものを使用することができ、チタン白、亜鉛黄、アルミナ白、シアニンブルー、等のシアニン系顔料、カーボンブラック、鉄黒、べんがら、黄色酸化鉄、モリブデートオレンジ、ハンサイエロー、ピラゾロンオレンジ、アゾ系顔料、紺青、縮合多環系顔料、などが例示できる。この他に、金属片・粉末・パール顔料、マイカ顔料、インジゴイド染料、硫化染料、フタロシアニン染料、ジフェニルメタン染料、ニトロ染料、アクリジン染料、等が挙げられる。有機被覆層中の顔料濃度は特に限定されず、必要な色や隠蔽力によって決定すればよい。
【００１７】
本発明の防食塗料は公知の方法で金属板の上に塗装される。金属板は密着性改善のための前処理を施す。例えば、リン酸亜鉛処理、シランカップリング処理、複合酸化被膜処理、タンニン酸処理、これらの混合処理等が挙げられる。塗装方法としては、例えば、ロールコーター、カーテンコーター、静電塗装、スプレー塗装、浸漬塗装などである。その後、熱風、誘導加熱、近赤外、遠赤外、などの加熱によって乾燥・硬化される。有機被覆層の樹脂が電子線や紫外線で硬化するものであればこれらの照射によって硬化される。これらの併用であってもよい。
【００１８】
本発明の耐食性に優れた塗装金属板は、前述の防錆塗料を金属板上に塗布、硬化乾燥したものである。塗装金属板の下地金属板は特に限定するものではなく一般に公知の金属板を用いることができる。アルミ合金やマグネシウム合金などの合金でもよいし、他の金属をめっきした金属でも良い。本発明は特に鋼系の金属及びめっきを施した鋼において効果を発揮する。鋼成分は特に限定するものではなく、例えば、Ｔｉ，Ｎｂ，Ｂ等を添加したＩＦ鋼、Ａｌ−ｋ鋼、Ｃｒ含有鋼、ステンレス鋼、ハイテン鋼等が挙げられる。めっき鋼板としては、溶融亜鉛めっき鋼板、溶融亜鉛−鉄合金めっき鋼板、溶融亜鉛−アルミニウム合金めっき鋼板、溶融亜鉛−マグネシウム合金めっき鋼板、溶融亜鉛−アルミニウム−マグネシウム合金めっき鋼板、溶融アルミニウム−シリコン合金めっき鋼板、溶融鉛−スズめっき鋼板などの溶融めっき鋼板、電気亜鉛めっき鋼板、電気亜鉛−ニッケルめっき鋼板、電気亜鉛−クロム合金めっき鋼板などの電気めっき鋼板等、Ｚｎ，Ａｌ，Ｍｇ，Ｓｎ，Ｎｉ，Ｃｕ，Ｐｂの１種以上から構成されるめっき層を有する鋼板が効果的である。
【００１９】
防食塗装の膜厚は０．２μｍ以上、１００μｍ未満である。０．２μｍ未満では耐食性の向上効果が不明確であり、１００μｍを越えると加工性が低下して厳しい加工で塗膜の割れが起こり、結果として耐食性が低下する。本発明の塗装金属板は本発明の防食塗料を塗装した上に着色した塗膜を施すことができる。着色塗料としては一般に公知のものを適用できる。例えば、ポリオレフィン樹脂、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、塩化ビニル樹脂、フッ素系樹脂、ブチラール樹脂、ポリカーボネート樹脂、フェノール樹脂などである。これらの混合物や共重合物も使用できる。また、これらにイソシアネート樹脂、アミノ樹脂、シランカップリング剤あるいはチタンカップリング剤等を補助成分として併用することができる。本発明によるプレコート金属板は加工後に補修をされずにそのまま使用されるケースが多いので、厳しい加工が施される用途では、ポリエステル樹脂をメラミンで架橋する樹脂系、ポリエステル樹脂をウレタン樹脂（イソシアネート、イソシアネート樹脂）で架橋する樹脂系、塩化ビニル樹脂系、フッ素樹脂系（溶剤可溶型、アクリル樹脂との分散混合型）が望ましい。着色は一般的な顔料や染料などによる。顔料としては、無機系、有機系、両者の複合系に関わらず公知のものを使用することができ、チタン白、亜鉛黄、アルミナ白、シアニンブルー、等のシアニン系顔料、カーボンブラック、鉄黒、べんがら、黄色酸化鉄、モリブデートオレンジ、ハンサイエロー、ピラゾロンオレンジ、アゾ系顔料、紺青、縮合多環系顔料、などが例示できる。この他に、金属片・粉末・パール顔料、マイカ顔料、インジゴイド染料、硫化染料、フタロシアニン染料、ジフェニルメタン染料、ニトロ染料、アクリジン染料、等が挙げられる。有機被覆層中の顔料濃度は特に限定されず、必要な色や隠蔽力によって決定すればよい。塗料としての形態は特に限定するものではなく、有機溶剤系塗料、水系塗料、コロイド分散系塗料、粉体塗料、電着塗料などが挙げられる。
【００２０】
着色された有機被覆層の膜厚は特に限定するものではないが、均一な外観を得るためには５μｍ以上の乾燥膜厚があることが望ましい。膜厚の上限はないが、コイルで連続的に塗装する場合は１回の塗装で乾燥膜厚が５０μｍ程度であることが多い、切り板に断続的に塗装する場合は焼き付けを緩やかな条件で行うことが可能であり、この上限膜厚は２００μｍ程度まで上がる。また、スプレー塗装などで１枚毎に処理する場合はさらに上限の膜厚は上がる。
【００２１】
本発明の塗装金属板は下塗り層として本発明以外の一般的な被膜層を施し、その上層に本発明の被膜層を施してもよい。
【００２２】
【実施例】
ピロリン酸、次リン酸、亜リン酸、次亜リン酸は市販の試薬を使用した。防錆塗料用のクリヤー塗料としては市販のポリエステル系クリヤー塗料、エポキシ系クリヤー塗料、ウレタン系クリヤー塗料を使用した。これらクリヤー塗料に各りんの酸素酸を各表に示す重量比で添加して、攪拌機で十分に撹拌した後に塗装を行った。
【００２３】
塗装を施す金属板としては亜鉛めっきの両面付着量が１２０ｇ／ｍ2 の溶融亜鉛めっき鋼板を用いた。板厚は０．６ｍｍである。溶融亜鉛めっき鋼板は脱脂を行い、水洗、乾燥した。次いで化成処理（下地処理）としてシランカップリング系処理（付着量２００ｍｇ／ｍ2 ）、リン酸亜鉛処理（１．８ｇ／ｍ2 ）、電解クロメート処理（全Ｃｒ付着量４５ｍｇ／ｍ2 ）のいずれかを施した。以上の処理を行った鋼板の両面に、上記防錆塗料をバーコーターで塗布し、熱風乾燥炉で到達板温２１０℃、到達時間４５秒間で焼き付け、そして水冷して防錆皮膜層を形成した。膜厚は各表に示した。
【００２４】
続いて、ポリエステル系上塗り塗料としてＦＬ１００ＨＱ（日本ペイント製、白色）をバーコーターで乾燥膜厚が１５μｍになるように塗布し、熱風乾燥炉で到達板温２２０℃、到達時間４５秒間で焼き付け、そして水冷して上層皮膜層を形成した。裏面は全て、メラミンアルキド系塗料を、バーコーターで乾燥膜厚が７μｍになるように塗布し、到達板温２３０℃、４５秒間の条件で焼き付け、そして水冷した。
【００２５】
比較材としてストロンチウムクロメートとカルシウムクロメートを防錆顔料として含有するものも作製した。
以上のようにして作製した塗装金属板に対して、カッターナイフを使用して評価面側（ポリエステル系上塗り塗装を施した面）の素地に到達するクロスカットを塗膜につけた後、ＪＩＳ−Ｋ５４００．９．１記載の方法で塩水噴霧試験を２４０時間実施した。塩水噴霧試験後にクロスカット片側の最大膨れ幅を測定して以下の基準で評点を付与した。
◎：片側膨れ幅１ｍｍ未満
○：片側膨れ幅１ｍｍ以上５ｍｍ未満
△：片側膨れ幅５ｍｍ以上
また、切断時の返り（バリ）が塗装鋼板の評価面側にくるように（上バリとなるように）作製した試験片についても上記の塩水噴霧試験を実施し、端面からの塗膜の膨れ幅を測定した。以下の基準で評点を付与した。
◎：端面からの膨れ幅３ｍｍ未満
○：端面からの膨れ幅３ｍｍ以上５ｍｍ未満
△：片側膨れ幅５ｍｍ以上
以下に評価結果の詳細を述べる。
【００２６】
表１〜１６に実験の詳細な条件と耐食性試験の結果を示す。本発明の防錆塗料を用いた塗装金属板（備考欄に本発明例と記入したもの）は耐食性に優れることがわかる。また、公知のクロム系防錆顔料であるストロンチウムクロメートとカルシウムクロメートを用いたものとほぼ同等の耐食性を有することがわかる。
【００２７】
【発明の効果】
本発明により、６価のクロム化合物を含まず、環境に優しい防錆塗料と耐食性に優れた塗装金属板を提供することが可能となる。
【００３２】
【表５】
【表６】
【表９】
【表１０】
【表１１】
【表１２】
【表１３】
【表１４】
【表１６】
BACKGROUND OF THE INVENTION
The present invention relates to a coated steel sheet. More specifically, the present invention relates to a coated metal plate that is excellent in corrosion resistance, has low toxicity because it does not contain toxic chromium, and is suitable for building materials and home appliances.
[0002]
[Prior art]
Instead of post-coated steel sheets that are coated after cutting and processing in fields such as home appliances and building materials, the amount of pre-coated steel sheets that have been coated before cutting and processing is increasing. This is because the use of a pre-coated steel sheet that is coated by a steel manufacturer eliminates the need for a home appliance manufacturer to have a coating line, and the pre-coated steel sheet has a smoother and more beautiful appearance than the post-coated steel sheet.
[0003]
In general, it is known that when severe processing is performed on a coated steel plate such as a pre-coated steel plate, the coating is damaged and the corrosion resistance is lowered. Moreover, since a bare steel plate will be exposed when a precoat steel plate is cut | disconnected, there exists a possibility that corrosion generate | occur | produces in the part. That is, the precoated steel sheet needs to have excellent corrosion resistance.
As an example of improving the corrosion resistance of such a pre-coated steel sheet, for example, JP-A-8-168723 discloses a technique for obtaining a pre-coated steel sheet having excellent workability, stain resistance and hardness by defining the structure of the film. It is disclosed. Japanese Patent Application Laid-Open No. 3-100180 discloses a precoated steel sheet having improved end face corrosion resistance by using a specific chromate treatment solution.
[0004]
In any case, a coated steel sheet with excellent corrosion resistance is subjected to a ground treatment called chromate treatment with excellent corrosion resistance and adhesion, and has an undercoat layer containing a chromium-based anticorrosive pigment with excellent corrosion resistance. It has a structure with a colored topcoat layer.
[0005]
[Problems to be solved by the invention]
The hexavalent chromium contained in the chromate treatment and the chromium-based anticorrosive pigment is water-soluble, and has the property of inhibiting corrosion of the zinc-based plated steel sheet when it is eluted. For example, even if the coating film is cracked by severe processing or when a bare steel plate is exposed at the cut part, it is extremely excellent in suppressing corrosion of that part. Widely used for pre-coated steel sheets.
[0006]
However, due to the toxicity of hexavalent chromium that may be eluted from the chromate treatment and the chromium-based anticorrosive pigment, recently there has been an increasing demand for a chromium-free base treatment and a chromium-free antirust pigment.
Therefore, the present invention has an object to provide a chromium-free low-toxic anticorrosion paint excellent in corrosion resistance and a coated metal plate treated with the paint in response to such a demand.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have made various studies on the corrosion resistance of the cut end face portions of various plated steel sheets under the conditions of various chromium-free primer treatments and various chromium-free primers. As a result, a low-toxic chromium-free pre-coated metal sheet having excellent end face corrosion resistance can be produced by applying a paint containing phosphoric acid instead of a chromium-based anti-corrosive pigment as an anti-corrosive paint. As a result, the present invention has been achieved.
[0008]
That is, the gist of the present invention is as follows.
(1) On at least one surface of the metal plate, one or more of pyrophosphoric acid, hypophosphoric acid, phosphorous acid, and hypophosphorous acid are added as a rust preventive additive in a total of 0.1 wt% or more and less than 40 wt% It has an anticorrosive paint, and has a coating film with a dry film thickness of 0.2 μm or more and less than 100 μm. Zinc phosphate treatment, silane coupling treatment, composite oxide film treatment, tannic acid treatment , coated metal plate having excellent corrosion resistance, characterized in that one of these mixtures treated.
[0009]
( 2 ) The coated metal plate having excellent corrosion resistance as described in ( 1 ) above, further having a colored coating film on the upper layer of the coating film made of the anticorrosion coating.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Thereafter, peak pyrophosphate of the present invention, hypophosphoric acid, phosphorous acid, will be referred to as oxygen acids of phosphorus are collectively hypophosphorous acid.
[0011]
The phosphorus oxyacid of the present invention can be used without any special pretreatment. The mechanism by which the corrosion resistance of the coated metal sheet is improved by using the oxygen acid of phosphorus of the present invention as a rust preventive additive has not been clarified, but is estimated as follows. That is, when the cut end surface of the coated metal plate of the present invention is easily corroded, that is, when it is placed in a wet environment, phosphate ions are eluted, and this phosphate ion reacts with the bare metal on the end surface and is stable. It is estimated that the formation of phosphate contributes to the improvement of corrosion resistance.
[0012]
The amount of phosphorus oxygen acid added to the anticorrosion paint of the present invention is 0.1 wt% or more, whether added alone or in a mixture of two or more. If it is less than 0.1 wt%, the effect of improving the corrosion resistance due to the addition is not recognized. Although not specifically set on the upper limit, since the film formation is difficult when it exceeds 40 wt%, and less than 40 wt%.
[0013]
The anticorrosion paint of the present invention is characterized by containing phosphorus oxyacid and a resin capable of film formation.
As the resin used in the anticorrosive paint of the present invention, generally known resins can be applied depending on the application. That is, polyolefin resin, acrylic resin, urethane resin, epoxy resin, polyester resin, vinyl chloride resin, fluorine resin, butyral resin, polycarbonate resin, phenol resin, and the like. Mixtures and copolymers of these can also be used. In addition, an isocyanate resin, an amino resin, a silane coupling agent, a titanium coupling agent, or the like can be used in combination as an auxiliary component.
[0014]
Since the precoated metal sheet according to the present invention is often used as it is without being repaired after processing, in applications where severe processing is performed, a resin system in which a polyester resin is crosslinked with melamine, a polyester resin is a urethane resin (isocyanate, A resin system that crosslinks with an isocyanate resin), a vinyl chloride resin system, or a fluororesin system (solvent soluble type, dispersion mixed type with acrylic resin) is desirable.
[0015]
The form as the paint is not particularly limited, and examples thereof include organic solvent paint, water paint, colloidal dispersion paint, powder paint, and electrodeposition paint.
The rust preventive paint of the present invention may contain other rust preventive pigments as required. Examples of rust preventive pigments include: (1) phosphate phosphate rust preventive pigments such as zinc phosphate, iron phosphate, aluminum phosphate, zinc phosphite, and (2) calcium molybdate, aluminum molybdate, molybdic acid. (3) vanadium rust preventive pigments such as vanadium oxide, (4) silicate pigments such as calcium silicate, (5) strontium chromate, zinc chromate, calcium chromate, potassium chromate, Chromate rust preventive pigments such as barium chromate, (6) fine silica such as water-dispersed silica, fumed silica, and the like can be used. However, since the chromate rust preventive pigment (5) is environmentally toxic, it is desirable to use other than these.
[0016]
The anticorrosive paint of the present invention may be colored as necessary. Coloring is based on common pigments and dyes. As the pigment, a known pigment can be used regardless of inorganic, organic, or a combination of both. Cyanine pigments such as titanium white, zinc yellow, alumina white, and cyanine blue, carbon black, and iron black Bengala, yellow iron oxide, molybdate orange, Hansa yellow, pyrazolone orange, azo pigments, bitumen, condensed polycyclic pigments, and the like. In addition, metal pieces, powders, pearl pigments, mica pigments, indigoid dyes, sulfur dyes, phthalocyanine dyes, diphenylmethane dyes, nitro dyes, acridine dyes, and the like can be given. The pigment concentration in the organic coating layer is not particularly limited, and may be determined according to the necessary color and hiding power.
[0017]
The anticorrosion paint of the present invention is applied on a metal plate by a known method. Metal plate to facilities preprocessing for the tight adhesion improvement. For example, zinc phosphate treatment, silane-coupling treatment, a composite oxide film treatment, tannic acid treatment, a mixed treatment. Examples of the coating method include a roll coater, a curtain coater, electrostatic coating, spray coating, and immersion coating. Thereafter, it is dried and cured by heating with hot air, induction heating, near infrared, far infrared, or the like. If the resin of the organic coating layer is hardened by an electron beam or ultraviolet rays, it is cured by these irradiations. These combinations may be used.
[0018]
The coated metal plate having excellent corrosion resistance according to the present invention is obtained by applying the above-mentioned rust preventive paint onto a metal plate and curing and drying it. The base metal plate of the painted metal plate is not particularly limited, and generally known metal plates can be used. An alloy such as an aluminum alloy or a magnesium alloy may be used, or a metal plated with another metal may be used. The present invention is particularly effective for steel-based metals and plated steel. The steel component is not particularly limited, and examples thereof include IF steel added with Ti, Nb, B, etc., Al-k steel, Cr-containing steel, stainless steel, and high-tensile steel. As galvanized steel sheets, hot dip galvanized steel sheets, hot dip zinc-iron alloy plated steel sheets, hot dip zinc-aluminum alloy plated steel sheets, hot dip zinc-magnesium alloy plated steel sheets, hot dip zinc-aluminum-magnesium alloy plated steel sheets, hot dip aluminum-silicon alloy plating Steel plate, hot dip galvanized steel plate such as galvanized lead-tin plated steel plate, electro galvanized steel plate, electro galvanized steel plate, electro galvanized steel plate such as electro zinc-chromium alloy galvanized steel plate, Zn, Al, Mg, Sn, Ni, etc. A steel plate having a plating layer composed of one or more of Cu and Pb is effective.
[0019]
The film thickness of the anticorrosion coating is 0 . 2 μm or more and less than 100 μm. If the thickness is less than 0.2 μm, the effect of improving the corrosion resistance is unclear. If the thickness exceeds 100 μm, the workability is lowered, and cracking of the coating film occurs due to severe processing, resulting in a decrease in corrosion resistance. The coated metal plate of the present invention can be coated with a colored coating film after the anticorrosive coating of the present invention is applied. As the coloring paint, generally known ones can be applied. For example, polyolefin resin, acrylic resin, urethane resin, epoxy resin, polyester resin, vinyl chloride resin, fluorine resin, butyral resin, polycarbonate resin, phenol resin, and the like. Mixtures and copolymers of these can also be used. In addition, an isocyanate resin, an amino resin, a silane coupling agent, a titanium coupling agent, or the like can be used in combination as an auxiliary component. Since the precoated metal sheet according to the present invention is often used as it is without being repaired after processing, in applications where severe processing is performed, a resin system in which a polyester resin is crosslinked with melamine, a polyester resin is a urethane resin (isocyanate, A resin system that crosslinks with an isocyanate resin), a vinyl chloride resin system, or a fluororesin system (solvent soluble type, dispersion mixed type with acrylic resin) is desirable. Coloring is based on common pigments and dyes. As the pigment, a known pigment can be used regardless of inorganic, organic, or a combination of both. Cyanine pigments such as titanium white, zinc yellow, alumina white, and cyanine blue, carbon black, and iron black Bengala, yellow iron oxide, molybdate orange, Hansa yellow, pyrazolone orange, azo pigments, bitumen, condensed polycyclic pigments, and the like. In addition, metal pieces, powders, pearl pigments, mica pigments, indigoid dyes, sulfur dyes, phthalocyanine dyes, diphenylmethane dyes, nitro dyes, acridine dyes, and the like can be given. The pigment concentration in the organic coating layer is not particularly limited, and may be determined according to the necessary color and hiding power. The form as the paint is not particularly limited, and examples thereof include organic solvent paint, water paint, colloidal dispersion paint, powder paint, and electrodeposition paint.
[0020]
The thickness of the colored organic coating layer is not particularly limited, but a dry film thickness of 5 μm or more is desirable in order to obtain a uniform appearance. There is no upper limit on the film thickness, but when coated continuously with a coil, the dry film thickness is often about 50 μm with a single coating. This upper limit film thickness can be increased to about 200 μm. In addition, the upper limit film thickness is further increased in the case of processing each sheet by spray coating or the like.
[0021]
The coated metal plate of the present invention may be provided with a general coating layer other than the present invention as an undercoat layer, and the coating layer of the present invention may be applied thereon.
[0022]
【Example】
Pi pyrophosphate, hypophosphoric acid, phosphorous acid, hypophosphorous acid was used commercially available reagents. Commercially available polyester-based clear paints, epoxy-based clear paints, and urethane-based clear paints were used as clear coatings for rust-preventive paints. The oxygen acid of each phosphorus was added to these clear paints at a weight ratio shown in each table, and after sufficiently stirring with a stirrer, coating was performed.
[0023]
As the metal plate to be coated, a hot dip galvanized steel sheet having a galvanized double-side adhesion amount of 120 g / m 2 was used. The plate thickness is 0.6 mm. The hot dip galvanized steel sheet was degreased, washed with water and dried. Next, any of silane coupling treatment (adhesion amount 200 mg / m 2 ), zinc phosphate treatment (1.8 g / m 2 ), and electrolytic chromate treatment (total Cr adhesion amount 45 mg / m 2 ) as chemical conversion treatment (primary treatment) I gave it. The anticorrosion paint was applied to both surfaces of the steel plate subjected to the above treatment with a bar coater, baked in a hot air drying furnace at an ultimate plate temperature of 210 ° C. for an arrival time of 45 seconds, and cooled with water to form an anticorrosive film layer. . The film thickness is shown in each table.
[0024]
Subsequently, FL100HQ (manufactured by Nippon Paint Co., Ltd., white) as a polyester-based top coat was applied with a bar coater so that the dry film thickness was 15 μm, and baked in a hot air drying oven at an ultimate plate temperature of 220 ° C. for an arrival time of 45 seconds An upper film layer was formed by water cooling. All the back surfaces were coated with a melamine alkyd paint so as to have a dry film thickness of 7 μm with a bar coater, baked at a final plate temperature of 230 ° C. for 45 seconds, and cooled with water.
[0025]
As a comparative material, a material containing strontium chromate and calcium chromate as an antirust pigment was also prepared.
The coated metal plate produced as described above was applied with a crosscut that reached the substrate on the evaluation surface side (the surface on which the polyester-based topcoat was applied) using a cutter knife, and then JIS-K5400. The salt spray test was conducted for 240 hours by the method described in 9.1. After the salt spray test, the maximum swelling width on one side of the crosscut was measured, and a score was given according to the following criteria.
◎: One-side swollen width less than 1 mm ○: One-side swollen width of 1 mm or more and less than 5 mm Δ: One-side swollen width of 5 mm or more In addition, the return (burr) at the time of cutting is on the evaluation surface side of the coated steel sheet ( ) The above-mentioned salt spray test was performed on the prepared test piece, and the swollen width of the coating film from the end face was measured. Scores were assigned according to the following criteria.
：: Swelling width from end face less than 3 mm ○: Swelling width from end face from 3 mm to less than 5 mm Δ: One side swelling width from 5 mm to 5 mm
[0026]
Tables 1 to 16 show the detailed conditions of the experiment and the results of the corrosion resistance test. It can be seen that the coated metal plate using the anticorrosive paint of the present invention (the sample of the present invention written in the remarks column) is excellent in corrosion resistance. Moreover, it turns out that it has a corrosion resistance substantially equivalent to the thing using strontium chromate and calcium chromate which are well-known chromium type rust preventive pigments.
[0027]
【The invention's effect】
According to the present invention, it is possible to provide an environment-friendly rust preventive paint and a coated metal plate excellent in corrosion resistance that do not contain a hexavalent chromium compound.
[0032]
[Table 5]
[Table 6]
[Table 9]
[Table 10]
[Table 11]
[Table 12]
[Table 13]
[Table 14]
[Table 16]
Claims (2)
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| JP22651299A JP4550956B2 (en) | 1999-08-10 | 1999-08-10 | Painted metal plate with excellent anticorrosion paint and corrosion resistance |
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| JP22651299A JP4550956B2 (en) | 1999-08-10 | 1999-08-10 | Painted metal plate with excellent anticorrosion paint and corrosion resistance |
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| JP2001049152A JP2001049152A (en) | 2001-02-20 |
| JP4550956B2 true JP4550956B2 (en) | 2010-09-22 |
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| DE102006003956A1 (en) * | 2006-01-26 | 2007-08-02 | Degussa Gmbh | Production of a corrosion protection layer on a metal surface e.g. vehicle structure comprises applying a sol-gel composition to the metal surface, drying and/or hardening and applying a further layer and drying and/or hardening |
| WO2011041340A1 (en) * | 2009-09-30 | 2011-04-07 | Dow Global Technologies Inc. | Epoxy resin compositions |
| JP2013158766A (en) * | 2012-02-03 | 2013-08-19 | Eco Cosmo:Kk | Method of adjusting coarting underlayer of building to be coated |
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| JP2001049152A (en) | 2001-02-20 |
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