JP6168101B2 - Surface-treated steel sheet, method for producing the same, and resin-coated steel sheet using the same - Google Patents
Surface-treated steel sheet, method for producing the same, and resin-coated steel sheet using the same Download PDFInfo
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- JP6168101B2 JP6168101B2 JP2015105238A JP2015105238A JP6168101B2 JP 6168101 B2 JP6168101 B2 JP 6168101B2 JP 2015105238 A JP2015105238 A JP 2015105238A JP 2015105238 A JP2015105238 A JP 2015105238A JP 6168101 B2 JP6168101 B2 JP 6168101B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 89
- 239000010959 steel Substances 0.000 title claims description 89
- 229920005989 resin Polymers 0.000 title claims description 77
- 239000011347 resin Substances 0.000 title claims description 77
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000005260 corrosion Methods 0.000 claims description 55
- 230000007797 corrosion Effects 0.000 claims description 55
- 239000002313 adhesive film Substances 0.000 claims description 36
- 229910045601 alloy Inorganic materials 0.000 claims description 30
- 239000000956 alloy Substances 0.000 claims description 30
- 238000005868 electrolysis reaction Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 17
- 239000005011 phenolic resin Substances 0.000 claims description 14
- 235000011007 phosphoric acid Nutrition 0.000 claims description 13
- 229910017091 Fe-Sn Inorganic materials 0.000 claims description 10
- 229910017136 Fe—Ni—Sn Inorganic materials 0.000 claims description 10
- 229910017142 Fe—Sn Inorganic materials 0.000 claims description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 10
- 150000003016 phosphoric acids Chemical class 0.000 claims description 7
- 239000010408 film Substances 0.000 description 51
- 239000010410 layer Substances 0.000 description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- 239000002244 precipitate Substances 0.000 description 23
- 238000007747 plating Methods 0.000 description 20
- 229910000576 Laminated steel Inorganic materials 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000011572 manganese Substances 0.000 description 18
- 229910052720 vanadium Inorganic materials 0.000 description 18
- 230000007547 defect Effects 0.000 description 17
- 239000010949 copper Substances 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- 239000010960 cold rolled steel Substances 0.000 description 11
- 239000005029 tin-free steel Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 230000008018 melting Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- -1 and further Co Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005211 surface analysis Methods 0.000 description 6
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000007765 extrusion coating Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000002585 base Substances 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
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001153 fluoro group Chemical class F* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- JRFKUVDHIAAEOU-UHFFFAOYSA-N [F-].[F-].[F-].[F-].[F-].[F-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+] JRFKUVDHIAAEOU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RBFRVUKIVGOWND-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate Chemical compound [O-2].[V+4].[O-]S([O-])(=O)=O RBFRVUKIVGOWND-UHFFFAOYSA-L 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本発明は、表面に樹脂フィルムなどをラミネートする、または樹脂を含有する塗料を塗装することにより樹脂を被覆した後、主に缶などの容器に用いられる表面処理鋼板、特に、高温湿潤環境下において被覆された樹脂との密着性(以後、湿潤樹脂密着性と呼ぶ)に優れ、かつ被覆された樹脂が欠落しても優れた耐食性を示す表面処理鋼板、その製造方法およびこの表面処理鋼板に樹脂が被覆された樹脂被覆鋼板に関する。 The present invention is a surface-treated steel sheet mainly used for containers such as cans after laminating a resin film or the like on the surface or coating a resin-containing paint, particularly in a high-temperature and humid environment. Surface-treated steel sheet having excellent adhesion to the coated resin (hereinafter referred to as wet resin adhesion) and excellent corrosion resistance even when the coated resin is missing, its manufacturing method, and resin for this surface-treated steel sheet Relates to a resin-coated steel sheet coated with
飲料缶、食品缶、ペール缶や18リットル缶などの各種金属缶には、錫めっき鋼板やティンフリー鋼板と呼ばれる電解クロム酸処理鋼板などの金属板が用いられている。なかでも、ティンフリー鋼板は、6価Crを含むめっき浴中で鋼板を電解処理することにより製造され、塗料など樹脂に対して優れた湿潤樹脂密着性を有していることに特長がある。 Various metal cans such as beverage cans, food cans, pail cans and 18 liter cans use metal plates such as electrolytic chromic acid treated steel plates called tin-plated steel plates or tin-free steel plates. Among these, tin-free steel sheets are manufactured by electrolytically treating steel sheets in a plating bath containing hexavalent Cr, and are characterized by excellent wet resin adhesion to resins such as paints.
近年、環境に対する意識の高まりから、世界的に6価Crの使用が規制される方向に向かっており、6価Crのめっき浴を用いて製造されるティンフリー鋼板に対してもその代替材が求められている。 In recent years, due to the increasing awareness of the environment, the use of hexavalent Cr has been regulated worldwide, and there is an alternative material for tin-free steel plates manufactured using a hexavalent Cr plating bath. It has been demanded.
一方、各種金属缶は、従来より、ティンフリー鋼板などの金属板に塗装を施した後に、缶体に加工して製造されていたが、近年、製造に伴う廃棄物の抑制のために、塗装に代わってプラスティックフィルムなどの樹脂を被覆した樹脂被覆金属板を缶体に加工する方法が多用されるようになっている。この樹脂被覆金属板には、樹脂が金属板に強く密着していることが必要であり、特に飲料缶や食品缶として用いられる樹脂被覆金属板には、内容物の充填後にレトルト殺菌工程を経る場合があるため、高温の湿潤環境下でも樹脂が剥離することのない優れた湿潤樹脂密着性と、引っ掻きなどで部分的に樹脂が欠落した場合でも、缶の内容物などに侵されて穴開きが生ずることのない優れた耐食性とが要求されている。 On the other hand, various types of metal cans have been manufactured by processing metal cans such as tin-free steel sheets and then processing them into cans. Instead of this, a method of processing a resin-coated metal plate coated with a resin such as a plastic film into a can body is frequently used. In this resin-coated metal plate, it is necessary that the resin is strongly adhered to the metal plate. In particular, the resin-coated metal plate used as a beverage can or a food can is subjected to a retort sterilization process after filling the contents. In some cases, the resin does not exfoliate even in a high-humidity environment, and even if the resin is partially lost due to scratching, the contents of the can are damaged and the hole is opened. There is a demand for excellent corrosion resistance that does not cause the occurrence of corrosion.
こうした要請に応じて、本発明者等は、最近、特許文献1に、鋼板の少なくとも片面に、Ni層、Sn層、Fe-Ni合金層、Fe-Sn合金層およびFe-Ni-Sn合金層のうちから選ばれた少なくとも1層からなる耐食性皮膜を形成後、Tiを含むイオンを含有し、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素を含むイオンを含有する水溶液中で陰極電解処理して密着性皮膜を形成することにより、Crを用いず、極めて優れた湿潤樹脂密着性と優れた耐食性を有する表面処理鋼板を製造できることを提示した。 In response to such a request, the present inventors recently disclosed in Patent Document 1 a Ni layer, a Sn layer, a Fe—Ni alloy layer, a Fe—Sn alloy layer, and a Fe—Ni—Sn alloy layer on at least one surface of a steel plate. After forming a corrosion-resistant film consisting of at least one layer selected from the above, it contains ions containing Ti, and at least one metal selected from Co, Fe, Ni, V, Cu, Mn and Zn Presents that surface treatment steel sheets with excellent wet resin adhesion and excellent corrosion resistance can be produced without using Cr by forming an adhesion film by cathodic electrolysis in an aqueous solution containing ions containing elements. did.
しかしながら、特許文献1に記載された方法で製造された表面処理鋼板には、筋状の表面欠陥が発生する場合がある。
However, the surface-treated steel sheet produced by the method described in
本発明は、Crを用いず、優れた湿潤樹脂密着性と耐食性を有し、筋状の表面欠陥が発生することのない表面処理鋼板、その製造方法およびこの表面処理鋼板を用いた樹脂被覆鋼板を提供することを目的とする。 The present invention relates to a surface-treated steel sheet that does not use Cr, has excellent wet resin adhesion and corrosion resistance, and does not generate streak-like surface defects, a method for producing the same, and a resin-coated steel sheet using the surface-treated steel sheet The purpose is to provide.
本発明者等は、上記目的を達成すべく鋭意検討したところ、特許文献1における密着性皮膜を形成するに際し、Tiの代わりにZrを含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素を含有する水溶液中で陰極電解処理を施すことが効果的であることを見出した。
The present inventors diligently studied to achieve the above object, and in forming an adhesive film in
本発明は、このような知見に基づきなされたもので、鋼板の少なくとも片面に、Ni層、Sn層、Fe-Ni合金層、Fe-Sn合金層およびFe-Ni-Sn合金層のうちから選ばれた少なくとも1層からなる耐食性皮膜を有し、前記耐食性皮膜上に、Zrを含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素をその合計でZrに対する質量比で0.01〜10含有する密着性皮膜を有することを特徴とする表面処理鋼板を提供する。本発明の表面処理鋼板では、密着性皮膜が、さらにリン酸類由来のPおよび／またはフェノール樹脂由来のCをその合計でZrに対する質量比で0.01〜10含有することが好ましい。また、密着性皮膜のZr付着量が片面あたり3〜200mg/m2であることが好ましい。 The present invention has been made based on such knowledge, and at least one surface of a steel plate is selected from a Ni layer, a Sn layer, a Fe—Ni alloy layer, a Fe—Sn alloy layer, and a Fe—Ni—Sn alloy layer. A corrosion-resistant film composed of at least one layer, containing Zr on the corrosion-resistant film, and further containing at least one metal element selected from Co, Fe, Ni, V, Cu, Mn, and Zn. There is provided a surface-treated steel sheet characterized by having an adhesive film containing 0.01 to 10 in terms of mass ratio to Zr in total. In the surface-treated steel sheet of the present invention, it is preferable that the adhesive film further contains P derived from phosphoric acids and / or C derived from a phenol resin in a total mass ratio of 0.01 to 10 with respect to Zr. Further, the Zr adhesion amount of the adhesive film is preferably 3 to 200 mg / m 2 per side.
本発明の表面処理鋼板は、鋼板の少なくとも片面に、Ni層、Sn層、Fe-Ni合金層、Fe-Sn合金層およびFe-Ni-Sn合金層のうちから選ばれた少なくとも1層からなる耐食性皮膜を形成後、Zrを0.008〜0.07モル/l(l:リットル)含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素をその合計でZrに対するモル比で0.01〜10含む水溶液中で、電気量密度1〜20C/dm2で陰極電解処理して密着性皮膜を形成することにより製造できる。 The surface-treated steel sheet of the present invention comprises at least one layer selected from a Ni layer, a Sn layer, a Fe—Ni alloy layer, a Fe—Sn alloy layer, and a Fe—Ni—Sn alloy layer on at least one side of the steel sheet. After forming the corrosion-resistant film, it contains 0.008 to 0.07 mol / l (l: liter) of Zr, and further contains at least one metal element selected from Co, Fe, Ni, V, Cu, Mn and Zn. In an aqueous solution containing 0.01 to 10 in molar ratio to Zr, an adhesive film can be formed by cathodic electrolysis at an electric density of 1 to 20 C / dm 2 .
本発明の表面処理鋼板は、また、鋼板の少なくとも片面に、Ni層、Sn層、Fe-Ni合金層、Fe-Sn合金層およびFe-Ni-Sn合金層のうちから選ばれた少なくとも1層からなる耐食性皮膜を形成後、Zrを0.008〜0.07モル/l含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素をその合計でZrに対するモル比で0.01〜10含む水溶液中において、電流密度が、Zrが析出する電流密度とZrが析出しない電流密度との間を周期0.01〜0.4秒で変化し、1周期当りのZrが析出しない電流密度にある時間が0.005〜0.2秒である電流を用い、サイクル数が10以上で、Zrが析出する電流密度における全電気量密度が3〜20C/dm2となる電解条件で陰極電解処理して密着性皮膜を形成することにより製造できる。ここで、Zrが析出しない電流密度の上限は、陰極電解処理に用いる水溶液の組成およびpHに依存する値である。この製造方法では、電流密度が、Zrが析出する電流密度とZrが析出しない電流密度との2値に変化する電流を用いることができる。このとき、Zrが析出しない電流密度を0A/dm2にすることが好ましい。 The surface-treated steel sheet of the present invention also has at least one layer selected from a Ni layer, a Sn layer, a Fe—Ni alloy layer, a Fe—Sn alloy layer, and a Fe—Ni—Sn alloy layer on at least one surface of the steel sheet. After forming a corrosion-resistant film comprising Zr in an amount of 0.008 to 0.07 mol / l, and at least one metal element selected from Co, Fe, Ni, V, Cu, Mn and Zn in total with respect to Zr In an aqueous solution containing 0.01 to 10 in molar ratio, the current density changes between the current density at which Zr precipitates and the current density at which Zr does not precipitate in a period of 0.01 to 0.4 seconds, and the current at which Zr per period does not precipitate Cathodic electrolytic treatment was performed using an electric current having a density in the range of 0.005 to 0.2 seconds under an electrolysis condition in which the number of cycles was 10 or more and the total electric density at the current density at which Zr was deposited was 3 to 20 C / dm 2. It can be manufactured by forming an adhesive film. Here, the upper limit of the current density at which Zr does not precipitate is a value depending on the composition and pH of the aqueous solution used for the cathodic electrolysis. In this manufacturing method, it is possible to use a current whose current density changes to a binary value of a current density at which Zr is deposited and a current density at which Zr is not deposited. At this time, the current density at which Zr does not precipitate is preferably 0 A / dm 2 .
上記したいずれの製造方法においても、陰極電解処理に用いる水溶液が、さらにリン酸類および／またはフェノール樹脂をその合計でZrに対するモル比で0.01〜10含有することが好ましい。 In any of the above production methods, the aqueous solution used for the cathodic electrolysis treatment preferably further contains phosphoric acids and / or phenol resins in a total molar ratio of 0.01 to 10 with respect to Zr.
本発明は、また、本発明の表面処理鋼板に樹脂が被覆されている樹脂被覆鋼板を提供する。 The present invention also provides a resin-coated steel sheet in which the surface-treated steel sheet of the present invention is coated with a resin.
本発明により、Crを用いず、優れた湿潤樹脂密着性と耐食性を有し、筋状の表面欠陥が発生することのない表面処理鋼板を製造できるようになった。本発明の表面処理鋼板は、これまでのティンフリー鋼板の代替材として問題なく、油、有機溶剤、塗料などを内容物とする容器に樹脂被覆することなく使用できる。また、樹脂を被覆して樹脂被覆鋼板とし、缶や缶蓋に加工してレトルト雰囲気に暴露しても、樹脂の剥離が生じない。また、引っかき傷などの樹脂の欠落部においても、素地であるFeの溶出が著しく少なく、耐食性にも極めて優れている。 According to the present invention, it has become possible to produce a surface-treated steel sheet that has excellent wet resin adhesion and corrosion resistance and does not cause streak-like surface defects without using Cr. The surface-treated steel sheet of the present invention can be used without any problem as an alternative to conventional tin-free steel sheets without being coated with a resin on a container containing oil, organic solvent, paint, or the like. Further, even if the resin is coated to form a resin-coated steel sheet, processed into a can or can lid and exposed to a retort atmosphere, the resin does not peel off. Further, even in a resin missing portion such as a scratch, the dissolution of Fe as a base material is remarkably small, and the corrosion resistance is extremely excellent.
1) 表面処理鋼板
本発明の表面処理鋼板には、鋼板の少なくとも片面に、Ni層、Sn層、Fe-Ni合金層、Fe-Sn合金層およびFe-Ni-Sn合金層のうちから選ばれた少なくとも1層からなる耐食性皮膜を形成後、この耐食性皮膜上に、Zrを含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素を含有する密着性皮膜が形成されている。
1) Surface-treated steel sheet The surface-treated steel sheet of the present invention is selected from a Ni layer, a Sn layer, a Fe-Ni alloy layer, a Fe-Sn alloy layer, and a Fe-Ni-Sn alloy layer on at least one side of the steel sheet. After forming a corrosion-resistant film consisting of at least one layer, the corrosion-resistant film contains Zr, and further contains at least one metal element selected from Co, Fe, Ni, V, Cu, Mn and Zn. An adhesive film is formed.
素材の鋼板としては、一般的な缶用の低炭素冷延鋼板を用いることができる
1.1) 耐食性皮膜
鋼板表面に形成された耐食性皮膜は、下地鋼板と強固に結合し、樹脂被覆鋼板とされた後に引っ掻きなどで部分的に樹脂が欠落した場合でも、鋼板に優れた耐食性を付与するために、Ni層、Sn層、Fe-Ni合金層、Fe-Sn合金層およびFe-Ni-Sn合金層の単層あるいはそれらの多層からなる皮膜とする必要がある。Ni層の場合は、鋼板の片面あたりのNi付着量を200mg/m2以上とすることが好ましい。Fe-Ni合金層の場合は、鋼板の片面あたりのNi付着量を60mg/m2以上とすることが好ましい。Sn層またはFe-Sn合金層の場合は、鋼板の片面あたりのSn付着量を100mg/m2以上とすることが好ましい。Fe-Ni-Sn合金層の場合は、鋼板の片面あたりのNi付着量を50mg/m2以上、Sn付着量を100mg/m2以上とすることが好ましい。ここで、NiやSn付着量の測定は、蛍光X線による表面分析により行うことができる。
As the material steel plate, a general low carbon cold rolled steel plate for cans can be used.
1.1) Corrosion-resistant coating The corrosion-resistant coating formed on the surface of the steel plate is firmly bonded to the base steel plate and gives excellent corrosion resistance to the steel plate even if the resin is partially lost due to scratching after being formed into a resin-coated steel plate. Therefore, it is necessary to form a single layer of Ni layer, Sn layer, Fe—Ni alloy layer, Fe—Sn alloy layer, and Fe—Ni—Sn alloy layer or a film composed of those layers. In the case of the Ni layer, it is preferable that the Ni adhesion amount per one side of the steel sheet is 200 mg / m 2 or more. In the case of the Fe—Ni alloy layer, it is preferable that the Ni adhesion amount per one side of the steel sheet is 60 mg / m 2 or more. In the case of the Sn layer or the Fe—Sn alloy layer, it is preferable that the Sn adhesion amount per one side of the steel sheet is 100 mg / m 2 or more. In the case of the Fe—Ni—Sn alloy layer, it is preferable that the Ni adhesion amount per side of the steel sheet is 50 mg / m 2 or more and the Sn adhesion amount is 100 mg / m 2 or more. Here, the measurement of the adhesion amount of Ni or Sn can be performed by surface analysis using fluorescent X-rays.
こうした耐食性皮膜の形成は、含有される金属元素に応じた公知の方法で行える。 Such a corrosion-resistant film can be formed by a known method according to the contained metal element.
1.2) 密着性皮膜
耐食性皮膜上に、Zrを含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素をその合計でZrに対する質量比で0.01〜10、より好ましくは0.01〜2含有する密着性皮膜を形成することにより、優れた湿潤樹脂密着性が得られ、筋状の表面欠陥の発生を確実に防止できる。この原因は、現在のところ明らかではないが、こうした金属元素がZrを含む皮膜中に取り込まれることにより、緻密で、表面の凹凸が均一に分布した皮膜が形成されるためと考えられる。
1.2) Adhesive film On the corrosion-resistant film, Zr is included, and at least one metal element selected from Co, Fe, Ni, V, Cu, Mn, and Zn is added in a mass ratio of 0.01 to Zr in total. By forming an adhesive film containing ˜10, more preferably 0.01˜2, excellent wet resin adhesion can be obtained, and generation of streak-like surface defects can be reliably prevented. The reason for this is not clear at present, but it is thought that when such a metal element is incorporated into a film containing Zr, a dense film having a uniform distribution of surface irregularities is formed.
密着性皮膜が、さらにリン酸類由来のPおよび／またはフェノール樹脂由来のCをその合計でZrに対する質量比で0.01〜10含有することが好ましい。これは、密着性皮膜にリン酸類由来のPおよび／またはフェノール樹脂由来のCが含有されることにより密着性皮膜の被覆性がさらに向上し、耐食性が改善されるためである。被覆性が向上する原因は、現在のところ明らかではないが、密着性皮膜の内部に存在する水酸基、フェノール樹脂の水酸基またはリン酸類の水酸基と、耐食性皮膜表面に存在する水酸基とが脱水縮合し架橋することで、酸素原子を介して耐食性皮膜と密着性皮膜とが共有結合したことによると考えられる。 It is preferable that the adhesive film further contains P derived from phosphoric acids and / or C derived from a phenol resin in a total mass ratio of 0.01 to 10 with respect to Zr. This is because the coverage of the adhesive film is further improved and the corrosion resistance is improved by containing P derived from phosphoric acids and / or C derived from the phenol resin in the adhesive film. The reason why the coatability is improved is not clear at present. This is considered to be due to the covalent bond between the corrosion-resistant film and the adhesive film via oxygen atoms.
密着性皮膜のZr付着量は、鋼板の片面あたり3〜200mg/m2であることが好ましい。これは、Zr付着量が3mg/m2以上200mg/m2以下で湿潤樹脂密着性の改善と筋状の表面欠陥の発生防止の効果が十分に得られ、200mg/m2を超えるとその効果は飽和し、コスト高となるためである。より好ましくは20〜100mg/m2である。 The Zr adhesion amount of the adhesive film is preferably 3 to 200 mg / m 2 per one side of the steel plate. This, Zr coating weight, the effect of prevention of improvement and streaky surface defects of wet resin adhesion is sufficiently obtained at 3 mg / m 2 or more 200 mg / m 2 or less, when it exceeds 200 mg / m 2 the effect Is saturated and the cost is high. More preferably from 20 to 100 mg / m 2.
密着性皮膜のCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素の合計の付着量は、鋼板の片面あたり10〜200mg/m2とすることが好ましい。こうした金属元素の合計の付着量が10mg/m2以上200mg/m2以下であれば湿潤樹脂密着性に優れ、かつ筋状の表面欠陥のない皮膜を形成できる。 The total adhesion amount of at least one metal element selected from Co, Fe, Ni, V, Cu, Mn and Zn of the adhesive film may be 10 to 200 mg / m 2 per one side of the steel sheet. preferable. When the total adhesion amount of these metal elements is 10 mg / m 2 or more and 200 mg / m 2 or less, it is possible to form a film having excellent wet resin adhesion and having no streak-like surface defects.
密着性皮膜は、さらにOを含有することが好ましい。Oを含有することによりZrの酸化物を主体とする皮膜となり、湿潤樹脂密着性の改善や筋状の表面欠陥の発生防止により効果的なためである。 The adhesive film preferably further contains O. This is because the inclusion of O makes a film mainly composed of an oxide of Zr, which is effective in improving wet resin adhesion and preventing the occurrence of streaky surface defects.
なお、密着性皮膜のZrやCo、Fe、Ni、V、Cu、Mn、Zn、Pの付着量の測定は、蛍光X線による表面分析により行うことができる。密着性皮膜のC量は、全C量をガスクロマトグラフィーにより測定した値から鋼板中に含まれるC量をバックグラウンドとして差し引くことにより求めることができる。O量については、特に規定しないが、XPS(X線光電子分光分析装置)による表面分析でその存在を確認することができる。 The adhesion amount of Zr, Co, Fe, Ni, V, Cu, Mn, Zn, and P on the adhesive film can be measured by surface analysis using fluorescent X-rays. The amount of C in the adhesive film can be determined by subtracting the amount of C contained in the steel sheet as the background from the value obtained by measuring the total amount of C by gas chromatography. The amount of O is not particularly defined, but its presence can be confirmed by surface analysis using XPS (X-ray photoelectron spectrometer).
密着性皮膜の形成は、Zrを0.008〜0.07モル/l、好ましくは0.02〜0.05モル/l含み、さらにCo、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素をその合計でZrに対するモル比で0.01〜10、好ましくは0.01〜2.5、さらに好ましくは0.01〜2含む水溶液中で、電気量密度1〜20C/dm2で陰極電解処理することにより可能である。Zrの濃度が0.008モル/l未満では湿潤樹脂密着性に優れ、かつ筋状の表面欠陥のない皮膜を形成できない。一方、0.07モル/lを超えると水溶液中で安定な状態で存在することが難しくなり、Zr酸化物が生成するという問題が生じる。Co、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素の合計濃度がモル比で0.01未満では湿潤樹脂密着性に優れ、かつ筋状の表面欠陥のない皮膜を形成できない。一方、10を超えると効果は飽和し、コスト高となる。 The formation of the adhesive film comprises 0.008 to 0.07 mol / l, preferably 0.02 to 0.05 mol / l of Zr, and at least one selected from Co, Fe, Ni, V, Cu, Mn and Zn. This is possible by cathodic electrolysis at an electric density of 1 to 20 C / dm 2 in an aqueous solution containing a total of 0.01 to 10, preferably 0.01 to 2.5, more preferably 0.01 to 2 molar ratios of metal elements to Zr. is there. If the Zr concentration is less than 0.008 mol / l, it is impossible to form a film having excellent wet resin adhesion and no streak-like surface defects. On the other hand, when it exceeds 0.07 mol / l, it becomes difficult to exist in a stable state in an aqueous solution, and there arises a problem that Zr oxide is generated. If the total concentration of at least one metal element selected from Co, Fe, Ni, V, Cu, Mn, and Zn is less than 0.01 in molar ratio, the wet resin adhesion is excellent, and there are no streaky surface defects. A film cannot be formed. On the other hand, if it exceeds 10, the effect is saturated and the cost becomes high.
Zrを含む水溶液としては、フルオロジルコニウム酸イオンを含む水溶液、またはフルオロジルコニウム酸イオンおよびフッ素塩を含む水溶液が好適である。フルオロジルコニウム酸イオンを与える化合物としては、フッ化ジルコン水素酸、六フッ化ジルコン酸アンモニウム、六フッ化ジルコン酸カリウムなどを用いることができる。フッ素塩としては、フッ化ナトリウム、フッ化カリウム、フッ化銀、フッ化錫などを用いることができる。特に、六フッ化ジルコン酸カリウムを含む水溶液、あるいは六フッ化ジルコン酸カリウムおよびフッ化ナトリウムを含む水溶液は、効率良く均質な皮膜を形成できるので好適である。 As the aqueous solution containing Zr, an aqueous solution containing fluorozirconic acid ions or an aqueous solution containing fluorozirconic acid ions and a fluorine salt is suitable. Examples of compounds that give fluorozirconate ions include hydrofluoric zirconate, ammonium hexafluoride zirconate, and potassium hexafluorozirconate. As the fluorine salt, sodium fluoride, potassium fluoride, silver fluoride, tin fluoride, or the like can be used. In particular, an aqueous solution containing potassium hexafluorozirconate or an aqueous solution containing potassium hexafluorozirconate and sodium fluoride is preferable because a homogeneous film can be formed efficiently.
また、Co、Fe、Ni、V、Cu、MnおよびZnを与える化合物としては、硫酸コバルト、塩化コバルト、硫酸鉄、塩化鉄、硫酸ニッケル、硫酸銅、酸化硫酸バナジウム、硫酸亜鉛、硫酸マンガンなどを用いることができる。このとき、これらの金属元素は、その合計がZrに対するモル比で0.01〜10、好ましくは0.01〜2.5、さらに好ましくは0.01〜2となるように添加される。 The compounds that give Co, Fe, Ni, V, Cu, Mn and Zn include cobalt sulfate, cobalt chloride, iron sulfate, iron chloride, nickel sulfate, copper sulfate, vanadium oxide sulfate, zinc sulfate, manganese sulfate, etc. Can be used. At this time, these metal elements are added so that the sum thereof is 0.01 to 10, preferably 0.01 to 2.5, and more preferably 0.01 to 2 in terms of a molar ratio to Zr.
陰極電解処理においては、電流密度を5〜20A/dm2、電解時間を1〜5secとして行えばよいが、電気量密度を3〜15C/dm2とすることが好ましい。 In the cathodic electrolysis treatment, the current density may be 5 to 20 A / dm 2 and the electrolysis time may be 1 to 5 seconds, but the electrical density is preferably 3 to 15 C / dm 2 .
さらに、陰極電解処理を、電流密度が、Zrが析出する電流密度とZrが析出しない電流密度との間を周期的に変化する電流を用いて皮膜の成長を断続的に行うと、一定電流で連続的に電解する場合に比べてより優れた湿潤樹脂密着性が得られる。そのためには、ある程度のZr付着量を確保する必要があるが、商業ベースに乗る生産性(ラインスピード)で必要なZr付着量を確保するには、周期が0.01〜0.4秒で、1周期当りのZrが析出しない電流密度にある時間が0.005〜0.2秒である電流を用い、サイクル数が10以上で、Zrが析出する電流密度における全電気量密度が3〜20C/dm2となる電解条件で陰極電解処理を行うことが好ましい。こうした条件で電解処理を行うことにより、Zrが析出しない電流密度では、Zrの析出が起こらないというよりむしろ析出したZrの再溶解が促進されるため、より緻密で、表面の凹凸がより均一に分布した皮膜が形成され、優れた湿潤樹脂密着性が得られると考えられる。 Further, when the cathode electrolysis treatment is carried out intermittently using a current that periodically changes between a current density at which Zr is deposited and a current density at which Zr is not deposited, Better wet resin adhesion is obtained compared to the case of continuous electrolysis. To that end, it is necessary to secure a certain amount of Zr adhesion, but in order to ensure the amount of Zr adhesion required for productivity (line speed) riding on a commercial base, the cycle is 0.01 to 0.4 seconds per cycle. Electrolysis conditions in which the current density at which Zr does not precipitate is 0.005 to 0.2 seconds, the cycle number is 10 or more, and the total electric quantity density at the current density at which Zr precipitates is 3 to 20 C / dm 2 It is preferable to perform cathodic electrolysis. By performing the electrolytic treatment under these conditions, the current density at which Zr does not precipitate promotes re-dissolution of the precipitated Zr rather than causing Zr to precipitate. It is considered that a distributed film is formed and excellent wet resin adhesion is obtained.
Zrが析出しない電流密度の上限、すなわちZrが析出しない場合とZrが析出する場合の境界の電流密度は、Zrや、Co、Fe、Ni、V、Cu、MnおよびZnのうちから選ばれた少なくとも1種の金属元素を含む水溶液の組成およびpHに依存する。例えば、図1には、六フッ化ジルコン酸カリウム12.5g/lおよび硫酸コバルト7水和物5g/lを含むpH4の水溶液中における電流密度とZr付着量との関係を示したが、この場合は0.8A/dm2以下ではZrの析出が起こらないことがわかる。このように、Zrが析出しない電流密度の上限は、陰極電解処理に用いる水溶液の組成やpHに依存するので、用いる水溶液に応じて予め求めておく必要がある。
The upper limit of the current density at which Zr does not precipitate, that is, the boundary current density when Zr does not precipitate and when Zr precipitates, was selected from Zr, Co, Fe, Ni, V, Cu, Mn, and Zn Depends on the composition and pH of the aqueous solution containing at least one metal element. For example, FIG. 1 shows the relationship between the current density and the amount of Zr deposited in an aqueous solution at
Zrが析出する電流密度とZrが析出しない電流密度との間を周期的に変化する電流としては、サイン曲線のように周期的に変化する交流電流や、Zrが析出する電流密度とZrが析出しない電流密度との2値に変化するパルス電流を用いることができる。その他、直流電流に交流電流やパルス電流を重畳した電流を用いることもできる。なお、Zrが析出する電流密度とZrが析出しない電流密度との2値に変化するパルス電流を用いる場合は、Zrが析出しない電流密度を0A/dm2にすることが、用いる水溶液に応じてZrが析出しない電流密度の上限を予め求める必要がなくなるので、より好ましい。 The current that periodically changes between the current density at which Zr precipitates and the current density at which Zr does not precipitate include alternating current that periodically changes like a sine curve, current density at which Zr precipitates, and Zr precipitates. It is possible to use a pulse current that changes in binary with a current density that does not. In addition, a current obtained by superimposing an alternating current or a pulse current on a direct current can also be used. When using a pulse current that changes to a binary value of the current density at which Zr precipitates and the current density at which Zr does not precipitate, the current density at which Zr does not precipitate can be set to 0 A / dm 2 depending on the aqueous solution used. This is more preferable because it is not necessary to obtain the upper limit of the current density at which Zr does not precipitate.
本発明では、さらにリン酸類および／またはフェノール樹脂をその合計でZrに対するモル比で0.01〜10含有する水溶液中において、上記した陰極電解処理を行うことが好ましい。これは、リン酸類および／またはフェノール樹脂を含有する水溶液中において陰極電解処理を行うことにより、リン酸類由来のPおよび／またはフェノール樹脂由来のCを含有する密着性皮膜を形成でき、上記のように密着性皮膜の被覆性がさらに向上し、耐食性が改善されるためである。このとき、リン酸類を与える化合物としては、オルトリン酸や、同時に添加した金属元素のリン酸化合物でもよく、リン酸ニッケル、リン酸鉄、リン酸コバルト、リン酸ジルコニウムなどを用いることができる。フェノール樹脂としては、重量平均分子量が3000〜20000程度のものが好ましく、5000程度のものがより好ましい。また、フェノール樹脂には、アミノアルコール変性させることで水溶性を持たせてもよい。 In the present invention, it is preferable to perform the above-described cathodic electrolysis treatment in an aqueous solution further containing phosphoric acids and / or phenol resins in a total molar ratio of 0.01 to 10 with respect to Zr. This is because an adhesive film containing phosphoric acid-derived P and / or phenolic resin-derived C can be formed by cathodic electrolysis in an aqueous solution containing phosphoric acid and / or phenolic resin, as described above. This is because the coverage of the adhesive film is further improved and the corrosion resistance is improved. At this time, as a compound that gives phosphoric acid, orthophosphoric acid or a phosphoric acid compound of a metal element added at the same time may be used, and nickel phosphate, iron phosphate, cobalt phosphate, zirconium phosphate, and the like can be used. The phenol resin preferably has a weight average molecular weight of about 3000 to 20000, more preferably about 5000. In addition, the phenol resin may be water-soluble by modifying with amino alcohol.
2) 樹脂被覆鋼板(ラミネート鋼板)
本発明の表面処理鋼板上に、樹脂を被覆して樹脂被覆鋼板とすることができる。上述したように、本発明の表面処理鋼板は湿潤樹脂密着性に優れているため、この樹脂被覆鋼板は優れた耐食性と加工性を有する。
2) Resin coated steel sheet (laminated steel sheet)
A resin-coated steel sheet can be formed by coating a resin on the surface-treated steel sheet of the present invention. As described above, since the surface-treated steel sheet of the present invention is excellent in wet resin adhesion, this resin-coated steel sheet has excellent corrosion resistance and workability.
本発明の表面処理鋼板に被覆する樹脂としては、特に限定はなく、各種熱可塑性樹脂や熱硬化性樹脂を挙げることができる。例えば、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体、エチレン-アクリルエステル共重合体、アイオノマー等のオレフィン系樹脂フィルム、またはポリブチレンテレフタラート等のポリエステルフィルム、もしくはナイロン6、ナイロン6,6、ナイロン11、ナイロン12等のポリアミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム等の熱可塑性樹脂フィルムの未延伸または二軸延伸したものを用いることができる。積層の際に接着剤を用いる場合は、ウレタン系接着剤、エポキシ系接着剤、酸変性オレフィン樹脂系接着剤、コポリアミド系接着剤、コポリエステル系接着剤(厚さ:0.1〜5.0μm)等が好ましい。さらに熱硬化性塗料を、厚み0.05〜2μmの範囲で表面処理鋼板側、あるいはフィルム側に塗布し、これを接着剤とすることもできる。
There is no limitation in particular as resin coat | covered on the surface treatment steel plate of this invention, Various thermoplastic resins and thermosetting resin can be mentioned. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, polyester film such as polybutylene terephthalate, or nylon 6 A non-stretched or biaxially stretched thermoplastic resin film such as a polyamide film such as
さらに、フェノールエポキシ、アミノ-エポキシ等の変性エポキシ塗料、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-酢酸ビニル共重合体けん化物、塩化ビニル-酢酸ビニル-無水マレイン酸共重合体、エポキシ変性-、エポキシアミノ変性-、エポキシフェノール変性-ビニル塗料または変性ビニル塗料、アクリル塗料、スチレン-ブタジェン系共重合体等の合成ゴム系塗料等の熱可塑性または熱硬化性塗料を単独でまたは2種以上組合わせて用いることができる。 Furthermore, modified epoxy paint such as phenol epoxy, amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, epoxy-modified- , Epoxyamino-modified, Epoxyphenol-modified vinyl paint or modified vinyl paint, Acrylic paint, Thermoplastic paint such as synthetic rubber paint such as styrene-butadiene copolymer, or a combination of two or more They can be used together.
樹脂被覆層の厚みは3〜50μm、特に5〜40μmの範囲にあることが望ましい。これは、厚みが上記範囲を下回ると耐食性が不十分となり、厚みが上記範囲を上回ると加工性の点で問題を生じやすいためである。 The thickness of the resin coating layer is desirably 3 to 50 μm, particularly 5 to 40 μm. This is because if the thickness is less than the above range, the corrosion resistance becomes insufficient, and if the thickness exceeds the above range, problems are likely to occur in terms of workability.
表面処理鋼板への樹脂被覆層の形成は任意の手段で行うことができる。例えば、押出コート法、キャストフィルム熱接着法、二軸延伸フィルム熱接着法等により行うことができる。押出コート法の場合、表面処理鋼板の上に樹脂を溶融状態で押出コートして、熱接着させることにより製造することができる。すなわち、樹脂を押出機で溶融混練した後、T-ダイから薄膜状に押し出し、押し出された溶融樹脂膜を表面処理鋼板と共に一対のラミネートロール間に通して冷却下に押圧一体化させ、次いで急冷する。多層の樹脂被覆層を押出コートする場合には、各層用の押出機を複数使用し、各押出機からの樹脂流を多重多層ダイ内で合流させ、以後は単層樹脂の場合と同様に押出コートを行えばよい。また、一対のラミネートロール間に垂直に表面処理鋼板を通し、その両側に溶融樹脂ウエッブを供給することにより、表面処理鋼板両面に樹脂被覆層を形成させることができる。 Formation of the resin coating layer on the surface-treated steel sheet can be performed by any means. For example, it can be performed by an extrusion coating method, a cast film thermal bonding method, a biaxially stretched film thermal bonding method, or the like. In the case of the extrusion coating method, it can be produced by extrusion coating a resin on a surface-treated steel sheet in a molten state and thermally bonding the resin. That is, after the resin is melt-kneaded with an extruder, it is extruded from a T-die into a thin film, and the extruded molten resin film is passed through a pair of laminate rolls together with a surface-treated steel sheet to be pressed and integrated under cooling, and then rapidly cooled. To do. When extrusion coating a multi-layer resin coating layer, use multiple extruders for each layer, merge the resin streams from each extruder in a multi-layer die, and then extrude as in the case of a single layer resin. Just coat it. Moreover, a resin coating layer can be formed on both surfaces of a surface-treated steel sheet by passing a surface-treated steel sheet vertically between a pair of laminate rolls and supplying a molten resin web to both sides thereof.
こうした樹脂被覆鋼板は、側面継ぎ目を有するスリーピース缶やシームレス缶(ツーピース缶)に適用することができる。また、ステイ・オン・タブタイプのイージーオープン缶蓋やフルオープンタイプのイージーオープン缶蓋にも適用することができる。 Such a resin-coated steel sheet can be applied to three-piece cans and seamless cans (two-piece cans) having side seams. The present invention can also be applied to a stay-on-tab type easy open can lid and a full open type easy open can lid.
上述したところは、この発明の実施形態の一例を示したに過ぎず、請求の範囲内において種々の変更を加えることができる。 The above description is merely an example of an embodiment of the present invention, and various modifications can be made within the scope of the claims.
ティンフリー鋼板(TFS)の製造のために使用される冷間圧延ままの低炭素鋼の冷延鋼板(板厚0.2mm)の両面に、表1に示すめっき浴a、bを用いて、次のA〜Dの方法により耐食性皮膜を形成する。
A：冷延鋼板を、10vol%H2+90vol%N2雰囲気中で、700℃程度で焼鈍して、伸び率1.5%の調質圧延を行った後、アルカリ電解脱脂し、硫酸酸洗を施した後、めっき浴aを用いてNiめっき処理を施しNi層からなる耐食性皮膜を形成する。
B：冷延鋼板をアルカリ電解脱脂し、めっき浴aを用いてNiめっき処理を施した後、10vol%H2+90vol%N2雰囲気中で、700℃程度で焼鈍して、Niめっきを拡散浸透させた後、伸び率1.5%の調質圧延を行い、Fe-Ni合金層からなる耐食性皮膜を形成する。
C：冷延鋼板をアルカリ電解脱脂し、めっき浴aを用いてNiめっきを施した後、10vol%H2+90vol%N2雰囲気中で、700℃程度で焼鈍して、Niめっきを拡散浸透させ、伸び率1.5%の調質圧延を行った後、脱脂、酸洗し、めっき浴bを用いてSnめっき処理を施し、Snの融点以上に加熱保持する加熱溶融処理を施す。この処理により、Fe-Ni-Sn合金層とこの上層のSn層からなる耐食性皮膜を形成する。
D：冷延鋼板をアルカリ電解脱脂し、条件Aと同様に焼鈍、調質圧延した後、めっき浴bを用いてSnめっきを施した後、Snの融点以上に加熱保持する加熱溶融処理を施す。この処理により、Fe-Sn合金層とこの上層のSn層からなる耐食性皮膜を形成する。
Using plating baths a and b shown in Table 1 on both sides of cold-rolled cold-rolled steel sheets (thickness 0.2 mm) as cold-rolled steel used for the production of tin-free steel sheets (TFS), A corrosion-resistant film is formed by the methods A to D.
A: The cold-rolled steel sheet, with 10vol% H 2 + 90vol% N 2 atmosphere, was annealed at about 700 ° C., after temper rolling elongation of 1.5%, and the alkaline electrolytic degreasing and acid pickling After the application, Ni plating treatment is performed using the plating bath a to form a corrosion-resistant film composed of a Ni layer.
B: The cold-rolled steel sheet was alkali electrolytic degreasing, was subjected to Ni plating using a plating bath a, with 10vol% H 2 + 90vol% N 2 atmosphere, it was annealed at about 700 ° C., a Ni plating spread After the permeation, temper rolling with an elongation of 1.5% is performed to form a corrosion-resistant film composed of a Fe—Ni alloy layer.
C: The cold-rolled steel sheet was alkali electrolytic degreasing, was subjected to Ni plating using a plating bath a, with 10vol% H 2 + 90vol% N 2 atmosphere, was annealed at about 700 ° C., cementation Ni plating After temper rolling with an elongation rate of 1.5%, degreasing, pickling, Sn plating treatment using the plating bath b, and heat melting treatment for heating and holding above the melting point of Sn are performed. By this treatment, a corrosion-resistant film composed of an Fe—Ni—Sn alloy layer and an upper Sn layer is formed.
D: Alkaline electrolytic degreasing of the cold-rolled steel sheet, annealing and temper rolling in the same manner as in Condition A, followed by Sn plating using the plating bath b, followed by a heat-melting treatment that heats and maintains the melting point of Sn or higher . By this treatment, a corrosion-resistant film composed of the Fe—Sn alloy layer and the upper Sn layer is formed.
C、Dの処理において、加熱溶融処理によりSnめっきの一部は合金化する。合金化せず残存した純Sn残量については、表3〜5に示す。 In the treatment of C and D, a part of Sn plating is alloyed by heat melting treatment. Tables 3 to 5 show the remaining pure Sn remaining without alloying.
次いで、鋼板両面に形成された耐食性皮膜上に、表2〜5に示す陰極電解処理の条件で陰極電解を行い、乾燥して密着性皮膜を形成して表面処理鋼板No.1〜33を作製する。なお、表面処理鋼板No.1、16、19、22、29は、密着性皮膜にCo、Fe、Ni、V、Cu、MnおよびZnが含有されておらず、比較例である。No.30、31は耐食性皮膜を形成しておらず、比較例である。No.32、33は耐食性皮膜上に、Tiを含み、さらにVもしくはMnを含有する密着性皮膜を形成した比較例である。 Next, cathodic electrolysis is performed on the corrosion-resistant films formed on both surfaces of the steel sheet under the conditions of cathodic electrolysis shown in Tables 2 to 5, and dried to form an adhesive film to produce surface-treated steel sheets No. 1 to 33 To do. The surface-treated steel sheets No. 1, 16, 19, 22, and 29 are comparative examples in which the adhesive film does not contain Co, Fe, Ni, V, Cu, Mn, and Zn. Nos. 30 and 31 are comparative examples without forming a corrosion-resistant film. Nos. 32 and 33 are comparative examples in which an adhesive film containing Ti and further containing V or Mn is formed on the corrosion-resistant film.
そして、密着性皮膜のZr付着量およびTi付着量は、蛍光X線分析法により、それぞれ予め含有量を化学分析して求めた検量板と比較して求める。また、Co、Fe、Ni、V、Cu、MnおよびZnの含有量についてはZrおよびTiと同様の蛍光Ｘ線分析法、ならびに化学分析、オージェ電子分光分析および二次イオン質量分析から適宜測定方法を選択して求め、密着性皮膜に含有されるZrまたはTiに対するCo、Fe、Ni、V、Cu、MnおよびZnの質量比を評価する。また、Oは、No.1〜33のすべてについてXPSによる表面分析でその存在を確認することができる。 Then, the Zr adhesion amount and the Ti adhesion amount of the adhesive film are obtained by fluorescent X-ray analysis in comparison with a calibration plate obtained by chemical analysis of the content in advance. In addition, Co, Fe, Ni, V, Cu, Mn, and Zn contents are appropriately measured from X-ray fluorescence analysis similar to Zr and Ti, as well as chemical analysis, Auger electron spectroscopy, and secondary ion mass spectrometry. Is selected and the mass ratio of Co, Fe, Ni, V, Cu, Mn and Zn to Zr or Ti contained in the adhesive film is evaluated. O can be confirmed by XPS surface analysis for all of Nos. 1 to 33.
また、これらの表面処理鋼板No.1〜33の両面に、延伸倍率3.1×3.1、厚さ25μm、共重合比12mol%、融点224℃のイソフタル酸共重合ポリエチレンテレフタラートフィルムを用い、フィルムの二軸配向度(BO値)が150になるようなラミネート条件、すなわち鋼板の送り速度:40m/min、ゴムロールのニップ長:17mm、圧着後水冷までの時間:1秒でラミネートして、ラミネート鋼板No.1〜33を作製する。ここで、ニップ長とは、ゴムロールと鋼板が接する部分の搬送方向の長さのことである。そして、作製したラミネート鋼板No.1〜33について、下記の方法により、湿潤樹脂密着性、耐食性および筋状の表面欠陥の評価を行う。
湿潤樹脂密着性：温度130℃、相対湿度100%のレトルト雰囲気における180°ピール試験により湿潤樹脂密着性の評価を行う。180°ピール試験とは、図2の(a)に示すようなフィルム2を残して鋼板1の一部3を切り取った試験片(サイズ：30mm×100mm、表裏の二面をそれぞれn=1とし、各ラミネート鋼板についてn=2となる)を用い、図2の(b)に示すように、試験片の一端に重り4(100g)を付けてフィルム2側に180°折り返して30min間放置して行うフィルム剥離試験のことである。そして、図2の(c)に示す剥離長5を測定して評価し、各ラミネート鋼板について表裏二面の剥離長(n=2)の平均を求める。剥離長5は小さいほど、湿潤樹脂密着性が良好であるといえるが、剥離長5が20mm未満であれば、本発明の目的とする優れた湿潤樹脂密着性が得られていると評価する。
耐食性：ラミネート鋼板のラミネート面にカッターナイフを用い鋼板素地に達するカットを交差して施し、1.5質量%NaCl水溶液と1.5質量%クエン酸水溶液を同量ずつ混合した試験液80mlに浸漬し、55℃で9日間放置して、カット部の耐食性(表裏の二面をそれぞれn=1とし、各ラミネート鋼板についてn=2となる)を次のように評価し、○であれば耐食性が良好であるとする。
○：n=2とも腐食なし
×：n=2の1以上において腐食あり
筋状の表面欠陥：筋状模様の発生程度を目視で観察し、次のように評価した。
○：筋状模様が確認されない。
×：筋状模様が確認される。
In addition, an isophthalic acid copolymerized polyethylene terephthalate film having a draw ratio of 3.1 × 3.1, a thickness of 25 μm, a copolymerization ratio of 12 mol%, and a melting point of 224 ° C. was used on both surfaces of these surface-treated steel sheets No. 1 to 33. Lamination conditions such that the degree of axial orientation (BO value) is 150, that is, steel sheet feed speed: 40 m / min, rubber roll nip length: 17 mm, time from crimping to water cooling: 1 second, laminating in a laminated steel sheet No. .1 to 33 are produced. Here, the nip length is the length in the transport direction of the portion where the rubber roll and the steel plate are in contact. And about the produced laminated steel plates No. 1-33, wet resin adhesiveness, corrosion resistance, and a streak-like surface defect are evaluated by the following method.
Wet resin adhesion: Wet resin adhesion is evaluated by a 180 ° peel test in a retort atmosphere at a temperature of 130 ° C. and a relative humidity of 100%. The 180 ° peel test is a test piece (size: 30 mm x 100 mm, with both sides of the front and back sides set to n = 1, leaving a
Corrosion resistance: Cut the laminate surface of the laminated steel plate to reach the steel plate substrate using a cutter knife, and immerse it in 80 ml of a test solution in which 1.5% by mass NaCl aqueous solution and 1.5% by mass citric acid aqueous solution are mixed in equal amounts, 55 ° C And left for 9 days to evaluate the corrosion resistance of the cut part (where both the front and back surfaces are n = 1 and n = 2 for each laminated steel sheet) as follows. And
○: No corrosion at n = 2 ×: Corrosion-like surface defects at 1 or more of n = 2: The degree of occurrence of streak pattern was visually observed and evaluated as follows.
○: A streak pattern is not confirmed.
X: A streak pattern is confirmed.
結果を表6に示す。本発明例であるラミネート鋼板No.2〜15、17、18、20、21、23〜28では、いずれも優れた湿潤樹脂密着性と耐食性を示し、筋状の表面欠陥も認められない。これに対し、比較例であるラミネート鋼板No.1、16、19、22、29は、耐食性には問題ないが、湿潤樹脂密着性に劣っており、ラミネート鋼板No.30、31は湿潤樹脂密着性には問題ないが、耐食性に劣っている。ラミネート鋼板No.32、33は湿潤樹脂密着性や耐食性には問題ないが、表面に筋状模様が確認される。 The results are shown in Table 6. In the laminated steel sheets Nos. 2 to 15, 17, 18, 20, 21, and 23 to 28, which are examples of the present invention, all exhibit excellent wet resin adhesion and corrosion resistance, and no streak-like surface defects are observed. On the other hand, the laminated steel sheets No. 1, 16, 19, 22, and 29, which are comparative examples, have no problem with corrosion resistance, but have poor wet resin adhesion, and the laminated steel sheets No. 30 and 31 have wet resin adhesion. There is no problem with the properties, but the corrosion resistance is poor. Laminated steel plates Nos. 32 and 33 have no problem in wet resin adhesion and corrosion resistance, but a streak pattern is confirmed on the surface.
ティンフリー鋼板(TFS)の製造のために使用される冷間圧延ままの低炭素鋼の冷延鋼板(板厚0.2mm)の両面に、表1に示すめっき浴a、bを用いて、上記したA〜Dの方法により耐食性皮膜を形成する。C、Dの処理において、加熱溶融処理によりSnめっきの一部は合金化する。合金化せず残存した純Sn残量については、表7〜9に示す。 Using the plating baths a and b shown in Table 1 on both sides of the cold-rolled cold-rolled steel plate (sheet thickness 0.2 mm) as cold-rolled steel used for the production of tin-free steel plates (TFS), the above A corrosion-resistant film is formed by the methods A to D described above. In the treatment of C and D, a part of Sn plating is alloyed by heat melting treatment. Tables 7 to 9 show the remaining pure Sn remaining without alloying.
次いで、鋼板両面に形成された耐食性皮膜上に、表7〜9に示す陰極電解処理の条件で陰極電解を行い、乾燥して密着性皮膜を形成して表面処理鋼板No.34〜49を作製する。このとき、処理浴のpHは、水酸化カリウムなどのアルカリ溶液、硫酸などの酸性溶液により調整する。また、表面処理鋼板No.34〜45では、パルス電流を用い、Zrが析出しない電流密度は0A/dm2としている。一方、表面処理鋼板No.46、47では、パルス電流を用い、図1の結果に基づいて、Zrが析出しない電流密度が0A/dm2でない例(No.46)とその上限を超えた例(No.47)を挙げている。これらの表面処理鋼板のうち、No.38、45、47は、陰極電解処理の電解条件が好ましいパルス電流条件の範囲外にある。No.48、49は、Zrの代わりにTiを含む水溶液中で陰極電解処理を施す比較例である。 Next, cathodic electrolysis is performed on the corrosion-resistant film formed on both surfaces of the steel sheet under the conditions of cathodic electrolysis shown in Tables 7 to 9, and dried to form an adhesive film to produce surface-treated steel sheets No. 34 to 49 To do. At this time, the pH of the treatment bath is adjusted with an alkaline solution such as potassium hydroxide or an acidic solution such as sulfuric acid. In the surface-treated steel plates No. 34 to 45, a pulse current is used, and the current density at which Zr does not precipitate is 0 A / dm 2 . On the other hand, in the case of surface-treated steel plates No. 46 and 47, using pulse current, based on the results of FIG. 1, the current density at which Zr does not precipitate is not 0 A / dm 2 (No. 46) and the case where the upper limit is exceeded (No. 47). Among these surface-treated steel sheets, Nos. 38, 45, and 47 are outside the range of pulse current conditions in which the electrolysis conditions for cathodic electrolysis are preferable. Nos. 48 and 49 are comparative examples in which cathodic electrolysis is performed in an aqueous solution containing Ti instead of Zr.
そして、耐食性皮膜のNiやSn付着量や、密着性皮膜のZrやTiの付着量は、蛍光X線分析法により、それぞれ予め付着量を化学分析して求めた検量板と比較して求める。また、Co、Fe、V、Mnの付着量についてはZrやTiと同様の蛍光Ｘ線分析法、ならびに化学分析、オージェ電子分光分析および二次イオン質量分析から適宜測定方法を選択して求める。また、Oは、No.34〜49のすべてについてXPSによる表面分析でその存在を確認することができる。 Then, the adhesion amount of Ni and Sn in the corrosion-resistant film and the adhesion amount of Zr and Ti in the adhesion film are obtained by fluorescent X-ray analysis in comparison with a calibration plate obtained by chemical analysis of the adhesion amount in advance. Further, the adhesion amount of Co, Fe, V, and Mn is determined by appropriately selecting a measurement method from the same fluorescent X-ray analysis method as that of Zr and Ti, chemical analysis, Auger electron spectroscopy analysis, and secondary ion mass spectrometry. O can be confirmed by XPS surface analysis for all Nos. 34 to 49.
これらの表面処理鋼板No.34〜49の両面に、実施例1と同様にしてラミネート鋼板No.34〜49を作製する。そして、作製したラミネート鋼板No.34〜49について、実施例１と同様にして、湿潤樹脂密着性、耐食性および筋状の表面欠陥の評価を行う。 Laminated steel plates No. 34 to 49 are produced on both surfaces of these surface-treated steel plates No. 34 to 49 in the same manner as in Example 1. And about the produced laminated steel plates No. 34-49, it carries out similarly to Example 1, and evaluates wet resin adhesiveness, corrosion resistance, and a streak-like surface defect.
結果を表10に示す。本発明例である表面処理鋼板を用いるラミネート鋼板No.34〜47では、いずれも優れた湿潤樹脂密着性と耐食性を示し、筋状の表面欠陥も認められない。また、周期が0.01〜0.4秒で、1周期当りのZrが析出しない電流密度にある時間が0.005〜0.2秒である電流を用い、サイクル数が10以上で、Zrが析出する電流密度における全電気量密度が3〜20C/dm2となる電解条件で陰極電解処理を行うNo.34〜37、39〜44、46では湿潤樹脂密着性の剥離長が15mm以下であり、特に優れた湿潤樹脂密着性が得られる。これに対し、比較例であるラミネート鋼板No.48、49では、いずれも優れた湿潤樹脂密着性と耐食性を示しているが、筋状の表面欠陥が認められる。 The results are shown in Table 10. In the laminated steel plates No. 34 to 47 using the surface-treated steel plate as an example of the present invention, all show excellent wet resin adhesion and corrosion resistance, and no streak-like surface defects are recognized. In addition, a current having a period of 0.01 to 0.4 seconds and a current density at which the Zr per period is not deposited is 0.005 to 0.2 seconds, a cycle number of 10 or more, and the total electric current at the current density at which Zr is deposited In No. 34 to 37, 39 to 44, and 46 where cathodic electrolysis is performed under electrolysis conditions where the quantity density is 3 to 20 C / dm 2 , the wet resin adhesion peel length is 15 mm or less, and particularly excellent wet resin adhesion Sex is obtained. On the other hand, laminated steel sheets No. 48 and 49, which are comparative examples, both show excellent wet resin adhesion and corrosion resistance, but streak-like surface defects are observed.
ティンフリー鋼板(TFS)の製造のために使用される冷間圧延ままの低炭素鋼の冷延鋼板(板厚0.2mm)の両面に、表1に示すめっき浴a、bを用いて、上記したA〜Dの方法により耐食性皮膜を形成する。C、Dの処理において、加熱溶融処理によりSnめっきの一部は合金化する。合金化せず残存した純Sn残量については、表11、12に示す。 Using the plating baths a and b shown in Table 1 on both sides of the cold-rolled cold-rolled steel plate (sheet thickness 0.2 mm) as cold-rolled steel used for the production of tin-free steel plates (TFS), the above A corrosion-resistant film is formed by the methods A to D described above. In the treatment of C and D, a part of Sn plating is alloyed by heat melting treatment. Tables 11 and 12 show the remaining pure Sn remaining without alloying.
次いで、鋼板両面に形成された耐食性皮膜上に、表11、12に示す陰極電解処理の条件で陰極電解を行い、乾燥して密着性皮膜を形成して表面処理鋼板No.50〜60を作製する。このとき、処理浴のpHは、水酸化カリウムなどのアルカリ溶液、硫酸などの酸性溶液により調整する。また、表面処理鋼板No.54〜60では、パルス電流を用い、Zrが析出しない電流密度は0A/dm2としている。なお、処理浴中のフェノール樹脂には、重量平均分子量5000のフェノール樹脂を用いる。 Next, cathodic electrolysis is performed on the corrosion-resistant film formed on both surfaces of the steel sheet under the conditions of cathodic electrolysis shown in Tables 11 and 12, and dried to form an adhesive film to produce surface-treated steel sheets No. 50-60. To do. At this time, the pH of the treatment bath is adjusted with an alkaline solution such as potassium hydroxide or an acidic solution such as sulfuric acid. In the surface-treated steel plates No. 54 to 60, a pulse current is used, and the current density at which Zr does not precipitate is 0 A / dm 2 . A phenol resin having a weight average molecular weight of 5000 is used as the phenol resin in the treatment bath.
そして、耐食性皮膜のNiやSn付着量や、密着性皮膜のZr付着量は、蛍光X線分析法により、それぞれ予め含有量を化学分析して求めた検量板と比較して求める。また、Co、Pの含有量についてはZrと同様の蛍光Ｘ線分析法、ならびに化学分析、オージェ電子分光分析および二次イオン質量分析から適宜測定方法を選択して求め、密着性皮膜に含有されるZrに対するCo、Pの質量比を評価する。また、Oは、No.50〜60のすべてについてXPSによる表面分析でその存在を確認することができる。また、密着性皮膜のC量は全C量をガスクロマトグラフィーにより測定した値から鋼板中に含まれるC量をバックグラウンドとして差し引くことにより求める。 Then, the amount of Ni or Sn attached to the corrosion-resistant film and the amount of Zr attached to the adhesive film are obtained by fluorescent X-ray analysis in comparison with a calibration plate obtained by chemical analysis of the content in advance. The Co and P contents are determined by selecting an appropriate measurement method from X-ray fluorescence analysis similar to Zr, chemical analysis, Auger electron spectroscopic analysis, and secondary ion mass spectrometry, and are contained in the adhesive film. The mass ratio of Co and P to Zr is evaluated. Further, O can be confirmed by XPS surface analysis for all Nos. 50 to 60. Further, the C amount of the adhesive film is obtained by subtracting the C amount contained in the steel sheet as a background from the value obtained by measuring the total C amount by gas chromatography.
これらの表面処理鋼板No.50〜60の両面に、実施例1と同様にしてラミネート鋼板No.50〜60を作製する。そして、作製したラミネート鋼板No.50〜60について、実施例１と同様にして、湿潤樹脂密着性、耐食性および筋状の表面欠陥の評価を行う。 Laminated steel plates No. 50-60 are prepared on both surfaces of these surface-treated steel plates No. 50-60 in the same manner as in Example 1. And about the produced laminated steel plates No. 50-60, it carries out similarly to Example 1, and evaluates wet resin adhesiveness, corrosion resistance, and a streak-like surface defect.
結果を表13に示す。本発明例であるラミネート鋼板No.50〜60では、いずれも優れた湿潤樹脂密着性と耐食性を示し、筋状の表面欠陥も認められない。また、パルス電流を用いて陰極電解処理を行うNo.54〜60では湿潤樹脂密着性の剥離長が15mm以下であり、特に優れた湿潤樹脂密着性が得られる。なお、Zrを含む密着性皮膜には、耐食性試験後にカット部以外に点状錆が認められる場合があるが、本発明例のように、皮膜中にリン酸類由来のPやフェノール樹脂由来のCを含有させると、点状錆は全く認められない。 The results are shown in Table 13. In the laminated steel sheets No. 50 to 60, which are examples of the present invention, all exhibit excellent wet resin adhesion and corrosion resistance, and no streak-like surface defects are observed. In Nos. 54 to 60, in which cathodic electrolysis is performed using a pulse current, the peel length of the wet resin adhesion is 15 mm or less, and particularly excellent wet resin adhesion is obtained. In addition, in the adhesive film containing Zr, spot-like rust may be observed in addition to the cut part after the corrosion resistance test, but as in the present invention example, P derived from phosphoric acid in the film and C derived from the phenol resin When selenium is contained, no point-like rust is recognized.
1 鋼板
2 フィルム
3 鋼板の切り取った部位
4 重り
5 剥離長
1 Steel plate
2 film
3 Parts cut from steel plate
4 weights
5 Peel length
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