JP4872315B2 - Surface-treated steel sheet and method for producing the same, resin-coated steel sheet, can and can lid - Google Patents
Surface-treated steel sheet and method for producing the same, resin-coated steel sheet, can and can lid Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims description 109
- 239000010959 steel Substances 0.000 title claims description 109
- 229920005989 resin Polymers 0.000 title claims description 63
- 239000011347 resin Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 44
- 239000000956 alloy Substances 0.000 claims description 44
- 238000007747 plating Methods 0.000 claims description 43
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 229910052726 zirconium Inorganic materials 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000010960 cold rolled steel Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 13
- 229910017136 Fe—Ni—Sn Inorganic materials 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 229910017091 Fe-Sn Inorganic materials 0.000 claims description 11
- 229910017142 Fe—Sn Inorganic materials 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 58
- 239000010408 film Substances 0.000 description 48
- 230000007797 corrosion Effects 0.000 description 25
- 238000005260 corrosion Methods 0.000 description 25
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 22
- 239000003973 paint Substances 0.000 description 17
- 239000005029 tin-free steel Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052718 tin Inorganic materials 0.000 description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 239000005001 laminate film Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 238000007765 extrusion coating Methods 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 229910000576 Laminated steel Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000005856 abnormality Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- 229910018100 Ni-Sn Inorganic materials 0.000 description 2
- 229910018532 Ni—Sn Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000009924 canning Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 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
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010409 ironing Methods 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
- 238000003475 lamination Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 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
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 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
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- WBFZBNKJVDQAMA-UHFFFAOYSA-D dipotassium;zirconium(4+);pentacarbonate Chemical compound [K+].[K+].[Zr+4].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WBFZBNKJVDQAMA-UHFFFAOYSA-D 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) 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
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、電解クロム酸処理鋼板(ティンフリー鋼板、以後、TFSと呼ぶ)の代替材として好適な、クロムを用いず、プラスチックフィルムなどの樹脂との密着性(以後、樹脂密着性と呼ぶ)、耐錆性、耐食性に優れる表面処理鋼板およびその製造方法、ならびにこの表面処理鋼板を下地とした樹脂被覆鋼板、それを用いた缶および缶蓋に関する。 The present invention is suitable as an alternative to an electrolytic chromic acid-treated steel sheet (tin-free steel sheet, hereinafter referred to as TFS), does not use chromium, and adheres to a resin such as a plastic film (hereinafter referred to as resin adhesiveness). The present invention relates to a surface-treated steel sheet excellent in rust resistance and corrosion resistance, a method for producing the same, a resin-coated steel sheet based on this surface-treated steel sheet, a can and a can lid using the same.
飲料缶、食品缶、ペール缶や18リットル缶などの金属缶用材料には、錫めっき鋼板やTFSなどが用いられている。なかでも、TFSは、6価クロムを含む浴中で鋼板に電解処理を施すことにより製造され、塗装前の一次防錆性や塗料密着性に優れていることに特長がある。 Tin-plated steel sheets and TFS are used as materials for metal cans such as beverage cans, food cans, pail cans and 18 liter cans. Among these, TFS is manufactured by subjecting a steel sheet to electrolytic treatment in a bath containing hexavalent chromium, and is characterized by excellent primary rust prevention and paint adhesion before coating.
近年、環境に対する意識の高まりから、世界的に6価クロムの使用が規制される方向に向かっており、製造に6価クロム浴を用いるTFSに対しても代替材が求められている。クロムを用いないTFSの代替材として、特許文献1には、鋼板面にリン酸塩層が形成された容器用表面処理鋼板が提案されている。特許文献2には、鋼板面に、順次Ni-Fe合金層、Ni層、Ni-Sn層、非合金化Sn層の皮膜が形成された容器用表面処理鋼板が提案されている。また、特許文献3には、金属材料面にZr、O、Fを主成分とした無機表面処理層が形成された表面処理金属材料が提案されている。 In recent years, with the increasing awareness of the environment, the use of hexavalent chromium has been restricted worldwide, and alternative materials are also required for TFS that uses a hexavalent chromium bath for production. As an alternative to TFS that does not use chromium, Patent Document 1 proposes a surface-treated steel sheet for containers in which a phosphate layer is formed on the steel sheet surface. Patent Document 2 proposes a surface-treated steel sheet for containers in which a coating of a Ni—Fe alloy layer, a Ni layer, a Ni—Sn layer, and a non-alloyed Sn layer is sequentially formed on the steel plate surface. Patent Document 3 proposes a surface-treated metal material in which an inorganic surface treatment layer mainly composed of Zr, O, and F is formed on the metal material surface.
一方、上記の金属缶は、従来より、TFSなどの鋼板に塗装を施した後に、製缶加工により製造されていたが、近年、塗装工程で排出される有機溶剤などの規制のために、塗装に代わってプラスチックフィルムなどの樹脂をラミネートしたラミネート鋼板(樹脂被覆鋼板)を製缶加工する方法が多用されるようになっている。このラミネート鋼板には、フィルム下で鉄の腐食(溶出)が深さ方向に進行し、缶内容物のフレーバー性に悪影響を及ぼしたり、缶に穴を開けたりといった問題が生じないように、強い樹脂密着性が必要である。特に、飲料缶や食品缶として用いられるラミネート鋼板には、内容物充填後にレトルト処理工程を経る場合があるため、高温の湿潤環境でも樹脂が剥離することのない強い樹脂密着性が要求される。
しかしながら、特許文献1に記載の鋼板面にリン酸塩層が形成された容器用表面処理鋼板では、鋼板面に化成処理皮膜であるリン酸塩層のみしか形成されていなので、金属めっきに比べてバリア効果が低いためと思われるが、耐錆性や耐食性が劣ったり、レトルト処理工程における樹脂密着性が不十分である。特許文献2に記載の鋼板面に順次Ni-Fe合金層、Ni層、Ni-Sn層、非合金化Sn層の皮膜が形成された容器用表面処理鋼板では、NiとSnのみの合金層を形成させるためにNiをSnと同等量必要とし、コスト高となるばかりか、比較的多量の非合金化Sn層のために樹脂密着性が不十分である。特許文献3に記載の金属材料面にZr、O、Fを主成分とした無機表面処理層が形成された表面処理金属材料では、製缶加工前の樹脂密着性は良好であるが、製缶加工後の樹脂密着性や耐食性が不十分である。特許文献3によれば、金属材料基体としては各種表面処理鋼板やアルミニウムなどの軽金属材料などが使用されるとし、特に制限されないが、実用には鋼板用なのかアルミニウム用なのかによって要求される特性は異なる。したがって、金属材料基体自身、特に表面処理鋼板の場合、メッキ構成も重要な要素となり、特許文献3はスチール缶用途としては現行塗装溶接缶として使用されている薄目付けぶりきや、DI缶用(塗装缶)として使用されるノーリフローぶりきの化成処理として、現在使用されているクロメート処理に置き換えて用いる技術を開示するものである。薄目付けぶりきやノーリフローぶりきに特許文献3に開示されるZr、O、Fを主成分とした無機表面処理層を適用した場合、塗装缶用途としての性能は満足するが、TFS代替としてラミネート用表面処理鋼板として用いた場合には樹脂密着性が十分に得られない問題があった。さらに、特許文献3には、ラミネート用表面処理鋼板としてめっき無し(冷延鋼板)を用いた実施例も開示されているが、この場合、樹脂密着性には優れるものの、塗装缶として使用した場合には塗膜はじきや欠陥部での耐食性が十分に得られないため使用できないものであった。 However, in the surface-treated steel sheet for containers in which a phosphate layer is formed on the steel sheet surface described in Patent Document 1, only the phosphate layer that is a chemical conversion film is formed on the steel sheet surface, so compared to metal plating This is probably because the barrier effect is low, but the rust resistance and corrosion resistance are inferior, and the resin adhesion in the retort treatment process is insufficient. In the surface-treated steel sheet for containers in which the Ni-Fe alloy layer, Ni layer, Ni-Sn layer, and non-alloyed Sn layer coating are sequentially formed on the steel sheet surface described in Patent Document 2, an alloy layer composed of only Ni and Sn is used. In order to form it, Ni is required in the same amount as Sn, which increases the cost, and the resin adhesion is insufficient due to a relatively large amount of non-alloyed Sn layer. In the surface-treated metal material in which an inorganic surface treatment layer mainly composed of Zr, O, and F is formed on the surface of the metal material described in Patent Document 3, the resin adhesion before canning is good. Resin adhesion and corrosion resistance after processing are insufficient. According to Patent Document 3, various metallic materials such as various surface-treated steel plates and aluminum are used as the metal material base, and there is no particular limitation, but the characteristics required depending on whether it is for steel plates or aluminum for practical use Is different. Therefore, in the case of a metal material substrate itself, particularly a surface-treated steel plate, the plating configuration is also an important factor, and Patent Document 3 is used for steel tin cans for thin tinplate and DI cans that are currently used as welded cans for painting ( As a chemical conversion treatment of no-reflow tinplate used as a paint can), a technique used in place of the chromate treatment currently used is disclosed. When the inorganic surface treatment layer mainly composed of Zr, O, and F disclosed in Patent Document 3 is applied to light tinting and no reflow tinning, the performance as a paint can is satisfied, but as an alternative to TFS When used as a surface-treated steel sheet for laminating, there is a problem that sufficient resin adhesion cannot be obtained. Furthermore, Patent Document 3 also discloses an example using no plating (cold rolled steel sheet) as a surface-treated steel sheet for laminating, but in this case, although it is excellent in resin adhesion, when used as a coating can The coating film cannot be used because it does not provide sufficient corrosion resistance at creases and defective parts.
本発明は、TFSの代替材として好適な、クロムを用いず、樹脂密着性、耐錆性、耐食性に優れる表面処理鋼板およびその製造方法、ならびにこの表面処理鋼板に有機樹脂を被覆した樹脂被覆鋼板、それを用いた缶および缶蓋を提供することを目的とする。 The present invention provides a surface-treated steel sheet that is suitable as an alternative to TFS, does not use chromium, has excellent resin adhesion, rust resistance, and corrosion resistance, and a method for producing the same, and a resin-coated steel sheet in which the surface-treated steel sheet is coated with an organic resin. An object is to provide a can and a can lid using the same.
本発明者らは、クロムを用いず、樹脂密着性、耐錆性、耐食性に優れる表面処理鋼板について鋭意研究を重ねた結果、以下のことを見出した。
I)耐錆性や耐食性を向上させるには、鋼板面に、酸素や水分に対するバリア性の高いFe-Sn合金層や、Fe-Ni-Sn合金層などの金属めっき層を設けることが効果的である。
II)しかしながら、こうした金属めっき層は、樹脂密着性の観点からは、不十分であり、樹脂密着性の向上には、金属めっき層上にさらにZrおよびOを含有する皮膜の形成が効果的である。
As a result of earnest research on surface-treated steel sheets that are excellent in resin adhesion, rust resistance, and corrosion resistance without using chromium, the present inventors have found the following.
I) In order to improve rust resistance and corrosion resistance, it is effective to provide a metal plating layer such as Fe-Sn alloy layer and Fe-Ni-Sn alloy layer with high barrier property against oxygen and moisture on the steel plate surface. It is.
II) However, such a metal plating layer is insufficient from the viewpoint of resin adhesion, and formation of a film containing Zr and O on the metal plating layer is effective for improving resin adhesion. is there.
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、Sn量が0.01〜1.0g/m 2 であり、非合金化Sn量が0.1mg/m2未満のFe-Sn合金層を有し、前記Fe-Sn合金層上にZrおよびOを含有する皮膜を有する表面処理鋼板を提供する。 The present invention has been made based on such knowledge, Fe-Sn having an Sn content of 0.01 to 1.0 g / m 2 and an unalloyed Sn content of less than 0.1 mg / m 2 on at least one side of the steel sheet. A surface-treated steel sheet having an alloy layer and having a coating containing Zr and O on the Fe—Sn alloy layer is provided.
本発明は、また、鋼板の少なくとも片面に、Ni付着量が0.002〜0.1g/m 2 で、Sn量が0.01〜1.0g/m 2 であり、非合金化Sn量が0.1mg/m2未満のFe-Ni-Sn合金層を有し、前記Fe-Ni-Sn合金層上にZrおよびOを含有する皮膜を有する表面処理鋼板を提供する。 In the present invention, at least one surface of the steel sheet has a Ni adhesion amount of 0.002 to 0.1 g / m 2 , a Sn amount of 0.01 to 1.0 g / m 2 , and an unalloyed Sn amount of less than 0.1 mg / m 2. And a surface-treated steel sheet having a coating containing Zr and O on the Fe-Ni-Sn alloy layer.
これら本発明の表面処理鋼板では、合金層は、Snめっき処理を施した後、加熱溶融処理を施して形成するのが一般的であり、十分な加熱時間の確保が必要である。高速製造性の観点からは、Sn量は少な目の方が望ましく、0.01〜0.5g/m2がより好ましい。 The surface treated steel sheet of the present invention, alloy layer was subjected to Sn plating, to form by applying a heat-melting treatment are common, it is necessary to secure a sufficient heating time. From the viewpoint of high-speed manufacturability, a smaller Sn amount is desirable, and 0.01 to 0.5 g / m 2 is more preferable.
これら本発明の表面処理鋼板では、ZrおよびOを含有する皮膜のZr量が5〜200mg/m2であることが好ましい。 In these surface-treated steel sheets of the present invention, the Zr content of the coating containing Zr and O is preferably 5 to 200 mg / m 2 .
本発明は、さらに、これら本発明の表面処理鋼板のZrおよびOを含有する皮膜上に、有機樹脂が被覆されている樹脂被覆鋼板、それを用いた缶および缶蓋を提供する。 The present invention further provides a resin-coated steel sheet in which an organic resin is coated on a coating containing Zr and O of the surface-treated steel sheet of the present invention, a can and a can lid using the same.
上記の本発明の表面処理鋼板は、冷延鋼板に、焼鈍、調質圧延した後、Sn量が0.01〜1.0g/m2となるようにSnめっき処理を施した後、加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満とし、フッ化ジルコン酸カリウムおよび/またはフッ化ジルコン酸アンモニウムを含む水溶液中で陰極電解処理を施す方法、あるいは冷延鋼板の両面に、Ni付着量が0.002〜0.1g/m 2 となるようにNiめっき処理を施し、焼鈍、調質圧延を順次施した後、Sn量が0.01〜1.0g/m2となるようにSnめっき処理を施し、その後加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満とし、フッ化ジルコン酸カリウムおよび/またはフッ化ジルコン酸アンモニウムを含む水溶液中で陰極電解処理を施す方法により製造することが好ましい。 Surface-treated steel sheet of the present invention described above, the cold-rolled steel sheet, annealing, after temper rolling, after the Sn amount is subjected to Sn plating such that 0.01 to 1.0 g / m 2, subjected to heat melting treatment In this method, the amount of non-alloyed Sn is less than 0.1 mg / m 2 and cathodic electrolysis is performed in an aqueous solution containing potassium fluoride zirconate and / or ammonium zirconate fluoride, or both surfaces of cold-rolled steel are coated with Ni. Ni plating treatment is performed so that the amount is 0.002 to 0.1 g / m 2 , annealing and temper rolling are sequentially performed, and then Sn plating treatment is performed so that the Sn amount is 0.01 to 1.0 g / m 2 , Thereafter, a heat melting treatment is performed so that the amount of non-alloyed Sn is less than 0.1 mg / m 2 , and the cathode electrolytic treatment is performed in an aqueous solution containing potassium fluoride zirconate and / or ammonium fluoride zirconate. preferable.
本発明により、TFSの代替材として好適な、クロムを用いず、樹脂密着性、耐錆性、耐食性に優れる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に有機樹脂を被覆して樹脂被覆鋼板とし、缶や缶蓋に加工しても、樹脂の剥離が全く起こらず加工できる。 According to the present invention, it is possible to produce a surface-treated steel sheet that is suitable as a substitute for TFS and that is excellent in resin adhesion, rust resistance, and corrosion resistance without using chromium. Even if the surface-treated steel sheet of the present invention is coated with an organic resin to form a resin-coated steel sheet and processed into a can or a can lid, the resin can be processed without any separation.
1)表面処理鋼板
本発明の表面処理鋼板は、鋼板の少なくとも片面に、i)非合金化Sn量が0.1mg/m2未満のFe-Sn合金層が形成され、このFe-Sn合金層上にZrおよびOを含有する皮膜が形成されている鋼板、あるいは、ii)非合金化Sn量が0.1mg/m2未満のFe-Ni-Sn合金層が形成され、このFe-Ni-Sn合金層上にZrおよびOを含有する皮膜が形成されている鋼板である。
1) Surface-treated steel sheet The surface-treated steel sheet of the present invention is formed on at least one surface of the steel sheet, i) an Fe-Sn alloy layer having an unalloyed Sn content of less than 0.1 mg / m 2 is formed A steel sheet in which a film containing Zr and O is formed, or ii) an Fe-Ni-Sn alloy layer having an unalloyed Sn content of less than 0.1 mg / m 2 is formed, and this Fe-Ni-Sn alloy A steel sheet in which a film containing Zr and O is formed on the layer.
鋼板面に、緻密な構造でピンホールが少なく、酸素や水分に対するバリア性の高いFe-Sn合金層やFe-Ni-Sn合金層を設けると、鋼板の耐食性や耐錆性が向上する。また、Fe-Ni-Sn合金層は樹脂密着性の向上にも効果的である。 If a Fe—Sn alloy layer or Fe—Ni—Sn alloy layer having a dense structure with few pinholes and a high barrier property against oxygen and moisture is provided on the steel plate surface, the corrosion resistance and rust resistance of the steel plate are improved. Moreover, the Fe—Ni—Sn alloy layer is also effective in improving the resin adhesion.
Fe-Sn合金層やFe-Ni-Sn合金層に含有されるSn量は、0.01g/m2未満では合金層の被覆が不十分となる場合があり、1.0g/m2を超えると加熱溶融処理で非合金化Sn量を0.1mg/m2未満にすることが難しいことから、0.01〜1.0g/m2であることが好ましい。なお、合金層中のSn量は、JIS G 3303-1969に規定される電解剥離法によるぶりきのSn付着量試験方法により求めた。 Sn content contained in Fe-Sn alloy layer or Fe-Ni-Sn alloy layer is less than 0.01 g / m 2 may cover the alloy layer is insufficient, the heating exceeds 1.0 g / m 2 Since it is difficult to make the amount of non-alloyed Sn less than 0.1 mg / m 2 by melt treatment, it is preferably 0.01 to 1.0 g / m 2 . The amount of Sn in the alloy layer was determined by the tin adhesion amount test method for tin plating by the electrolytic stripping method specified in JIS G 3303-1969.
しかし、レトルト処理後や製缶加工後においても優れた樹脂密着性や耐食性を得るには、Fe-Sn合金層やFe-Ni-Sn合金層に(通常はそれら合金層の上層部に)含まれる非合金化Sn量を0.1mg/m2未満とし、かつFe-Sn合金層やFe-Ni-Sn合金層の上にZrおよびOを含有する皮膜を形成させる必要がある。ここで、非合金化Sn量が0.1mg/m2未満とは、上記JIS G 3303-1969に規定されるSn付着量試験方法で求めた電位-時間曲線において、合金化していない表面に存在するSnの溶解による停滞電位が無く、直ちに合金Sn溶解電位が現れる状態を表す。 However, in order to obtain excellent resin adhesion and corrosion resistance even after retorting and can manufacturing, it is included in the Fe-Sn alloy layer and Fe-Ni-Sn alloy layer (usually in the upper layer of these alloy layers). The amount of non-alloyed Sn must be less than 0.1 mg / m 2 , and a film containing Zr and O must be formed on the Fe—Sn alloy layer or Fe—Ni—Sn alloy layer. Here, the amount of non-alloyed Sn is less than 0.1 mg / m 2 is present on an unalloyed surface in the potential-time curve obtained by the Sn adhesion amount test method defined in JIS G 3303-1969. This represents a state in which there is no stagnation potential due to dissolution of Sn, and an alloy Sn dissolution potential immediately appears.
ZrおよびOを含有する皮膜のZr量は、5mg/m2未満だと樹脂との密着性改善の効果が不十分であり、200mg/m2を超えると更なる密着性の向上が望めず、コスト高となるので、5〜200mg/m2であることが好ましい。なお、この皮膜のZr量は、蛍光X線分析により、予め付着量既知のサンプルを測定して得た検量線により求めることができる。Zrの皮膜中の存在状態としては、Oと結合した酸化物であればよいが、この酸化物の下層側に金属状態として一部が存在していてもよい。また、O量については、特に規定しないが、X線光電子分光法(XPS)による表面分析でその存在を確認することができる。 Zr amount of coating containing Zr and O are insufficient effect of improving adhesion between the resin and less than 5 mg / m 2, not be expected further improvement in adhesion exceeds 200 mg / m 2, Since it becomes high in cost, it is preferable that it is 5-200 mg / m < 2 >. The Zr amount of this film can be obtained from a calibration curve obtained by measuring a sample with a known adhesion amount in advance by fluorescent X-ray analysis. The state of presence in the Zr film may be any oxide bonded to O, but a part of the metal may be present on the lower layer side of this oxide. The amount of O is not particularly defined, but its presence can be confirmed by surface analysis by X-ray photoelectron spectroscopy (XPS).
本発明の表面処理鋼板は、冷延鋼板に、焼鈍、調質圧延した後、Sn量が0.01〜1.0g/m2となるようにSnめっき処理を施し、加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満としたFe-Sn合金層を形成後、あるいは、冷延鋼板に、Niめっき処理、焼鈍、調質圧延を順次施し、Fe-Ni合金層を形成し、さらにSn量が0.01〜1.0g/m2となるようにSnめっき処理を施し、錫融点以上の温度に加熱保持することで合金化を促進する加熱溶融処理を施して非合金化Sn量を0.1mg/m2未満としたFe-Ni-Sn合金層を形成後、次に述べる方法でZrおよびOを含有する皮膜を形成させることにより製造できる。なお、Fe-Ni-Sn合金層を形成するには、冷延鋼板に、焼鈍、調質圧延した後、Niめっき処理し、Sn量が0.01〜1.0g/m2となるようにSnめっき処理を施し、上述のように加熱溶融処理を施してもよい。 The surface-treated steel sheet of the present invention is cold-rolled steel sheet, annealed and temper-rolled, then Sn-plated so that the Sn amount is 0.01 to 1.0 g / m 2, and heat-melted to be non-alloyed After forming the Fe-Sn alloy layer with an Sn amount of less than 0.1 mg / m 2 or by sequentially subjecting the cold-rolled steel sheet to Ni plating treatment, annealing and temper rolling to form an Fe-Ni alloy layer, The Sn plating treatment is performed so that the Sn amount is 0.01 to 1.0 g / m 2, and the heat melting treatment is performed to promote alloying by heating and holding at a temperature equal to or higher than the melting point of the tin, and the non-alloyed Sn amount is 0.1 mg. After forming a Fe—Ni—Sn alloy layer of less than / m 2, a film containing Zr and O can be formed by the method described below. In order to form the Fe-Ni-Sn alloy layer, the cold-rolled steel sheet is annealed and temper-rolled, then Ni-plated, and Sn-plated so that the Sn amount is 0.01 to 1.0 g / m 2. And may be heat-melted as described above.
ここで、Snめっき処理は、一般的に使用されているフェロスタン浴、ハロゲン浴、MSA浴等を用いて行えばよい。また、Niめっき処理は、一般的に用いられているワット浴、硫酸浴、スルファミン酸浴などのNiめっき浴を用いて行えばよく、Ni付着量は0.002〜0.1g/m2が好ましい。また、焼鈍は、還元性雰囲気中で連続焼鈍すればよく、650〜750℃の温度範囲に30sec〜10min保持して行うのが好ましい。さらに、調質圧延の伸び率は1.5〜2%が好ましい。 Here, the Sn plating treatment may be performed using a commonly used ferrostan bath, halogen bath, MSA bath or the like. Further, the Ni plating treatment may be performed using a commonly used Ni plating bath such as a watt bath, a sulfuric acid bath, a sulfamic acid bath, and the Ni adhesion amount is preferably 0.002 to 0.1 g / m 2 . Further, the annealing may be performed by continuous annealing in a reducing atmosphere, and is preferably carried out while maintaining at a temperature range of 650 to 750 ° C. for 30 seconds to 10 minutes. Furthermore, the elongation of temper rolling is preferably 1.5 to 2%.
ZrおよびOを含有する皮膜は、ジルコニウム酸塩水溶液中に鋼板を浸漬する方法、あるいは同液中で鋼板を電解処理する方法などにより形成できる。ジルコニウム酸塩としては、硫酸ジルコニウム、酢酸ジルコニウム、硝酸ジルコニウム、炭酸ジルコニウムアンモニウム、炭酸ジルコニウムカリウム、フッ化ジルコン酸カリウム、フッ化ジルコン酸アンモニウムなどを用いることができる。特に、フッ化ジルコン酸カリウムおよび/またはフッ化ジルコン酸アンモニウムの水溶液中で陰極電解処理する方法は、効率良く均質な皮膜を形成することが可能なので、好適である。 The film containing Zr and O can be formed by a method of immersing a steel plate in an aqueous zirconate solution, or a method of electrolytically treating a steel plate in the same solution. As the zirconium salt, zirconium sulfate, zirconium acetate, zirconium nitrate, ammonium zirconium carbonate, potassium zirconium carbonate, potassium fluoride zirconate, ammonium fluoride zirconate, or the like can be used. In particular, a method of cathodic electrolysis in an aqueous solution of potassium fluoride zirconate and / or ammonium fluoride zirconate is preferable because a homogeneous film can be efficiently formed.
2)樹脂被覆鋼板
本発明の表面処理鋼板のZrおよびOを含有する皮膜上に、有機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樹脂密着性や耐食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 The surface-treated steel sheet of the present invention can be made into a resin-coated steel sheet by coating an organic resin on the coating containing Zr and O. As described above, since the surface-treated steel sheet of the present invention is excellent in resin adhesion and corrosion resistance, 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有機樹脂としては、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、アイオノン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レ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であってもよい。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)等が好ましく用いられる。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、これを接着剤としてもよい。 The organic resin coated on the surface-treated steel sheet of the present invention is not particularly limited, and various thermoplastic resins and thermosetting resins can be exemplified. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyester film such as polybutylene terephthalate, or nylon 6, A non-stretched or biaxially stretched thermoplastic resin film such as a nylon film such as nylon 6,6, nylon 11, or nylon 12, a polyvinyl chloride film, or a polyvinylidene chloride film may be used. When using an adhesive during lamination, urethane adhesive, epoxy adhesive, acid-modified olefin resin adhesive, copolyamide adhesive, copolyester adhesive (thickness: 0.1 to 5.0 μm), etc. Is preferably used. Furthermore, a thermosetting paint may be applied to the surface-treated steel plate side or film side in a thickness range of 0.05 to 2 μm, and this may be used as an adhesive.
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の単独または2種以上の組合わせであってもよい。 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, Synthetic rubber paint such as styrene-butadiene copolymer, etc. It may be a combination.
本発明において、有機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。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。 In the present invention, the thickness of the organic resin coating layer is desirably 3 to 50 μm, particularly 5 to 40 μm. When the thickness is below the above range, the corrosion resistance becomes insufficient, and when the thickness is above the above range, problems are likely to occur in terms of workability.
本発明において、表面処理鋼板への有機樹脂被覆層の形成は任意の手段で行うことができ、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有機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、有機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。多層の有機樹脂被覆層を押出コートする場合には、表層樹脂用の押出機および下層樹脂用の押出機を使用し、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、前記表面処理鋼板両面に有機樹脂被覆層を形成させることができる。 In the present invention, the organic resin coating layer can be formed on the surface-treated steel sheet by any means, for example, 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 an organic resin in a molten state on a surface-treated steel plate and thermally bonding it. That is, after melt-kneading the organic resin 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 laminating rolls together with a surface-treated steel plate, and is pressed and integrated under cooling, Cool quickly. When extrusion coating a multilayer organic resin coating layer, an extruder for the surface layer resin and an extruder for the lower layer resin are used, and the resin flow from each extruder is merged in a multi-layer die, and thereafter Extrusion coating may be performed as in the case of the layer resin. Moreover, an organic resin coating layer can be formed on both surfaces of the surface-treated steel sheet by passing the surface-treated steel sheet vertically between a pair of laminate rolls and supplying a molten resin web to both sides thereof.
3)缶および缶蓋
本発明の缶は、前述した樹脂被覆鋼板から形成されている限り、任意の製缶法によるものでよい。この缶は、側面継ぎ目を有するスリーピース缶であることもできるが、一般にシームレス缶(ツーピース缶)であることが好ましい。このシームレス缶は、表面処理鋼板の有機樹脂の被覆面が缶内面側となるように、絞り・再絞り加工、絞り・再絞りによる曲げ伸ばし加工(ストレッチ加工)、絞り・再絞りによる曲げ伸ばし・しごき加工、あるいは絞り・しごき加工等の従来公知の手段に付すことによって製造される。
3) Can and can lid As long as the can of the present invention is formed from the above-mentioned resin-coated steel sheet, any can manufacturing method may be used. The can can be a three-piece can having a side seam, but is generally preferably a seamless can (two-piece can). This seamless can is drawn and redrawn, bent and stretched by drawing and redrawing (stretching), and stretched and drawn by drawing and redrawing so that the coated surface of the organic resin on the surface-treated steel sheet faces the inner surface of the can. It is manufactured by subjecting it to a conventionally known means such as ironing or drawing / ironing.
また、本発明の缶蓋は、上述した樹脂被覆鋼板から形成されている限り、従来公知の任意の製蓋法によるものでよい。一般には、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適用することができる。 Moreover, the can lid of this invention may be based on the conventionally well-known arbitrary lid-making method, as long as it is formed from the resin-coated steel plate mentioned above. In general, the present invention can 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 the embodiment of the present invention, and various modifications can be made within the scope of the claims.
TFSに使用される低炭素鋼の冷延鋼板(板厚:0.2mm)あるいは冷延鋼板(板厚:0.2mm)を焼鈍(10vol%H2+90vol%N2雰囲気中、700℃)後調質圧延(伸び率1.5%)した鋼板に、表1に示すめっき浴a〜cを用いて、次のA〜Dの方法により合金めっき層を両面に形成した。
A：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、10%H2+90%N2雰囲気中で、700℃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、錫の融点以上に加熱保持する加熱溶融処理を施した。
B：冷延鋼板を焼鈍後調質圧延した後、アルカリ電解脱脂し、硫酸酸洗後、めっき浴aを用いてNiめっき処理を施し、さらにめっき浴cを用いてSnめっき処理を施した後、錫の融点以上に加熱保持する加熱溶融処理を施した。
C：冷延鋼板を焼鈍後調質圧延した後、アルカリ電解脱脂し、硫酸酸洗後、めっき浴bを用いてSnめっき処理を施し、錫の融点以上に加熱保持する加熱溶融処理を施した。
D：冷延鋼板を焼鈍後調質圧延した後、アルカリ電解脱脂し、硫酸酸洗後、めっき浴bを用いてSnめっき処理を施し、錫の融点以上に加熱保持する加熱溶融処理を施し、引き続き10g/lの炭酸水素ナトリウム水溶液中において電流蜜5A/dm2で陰極電解処理を施した。
Low-carbon steel cold-rolled steel sheet (thickness: 0.2 mm) or cold-rolled steel sheet (thickness: 0.2 mm) used for TFS is annealed (10 vol% H 2 +90 vol% N 2 atmosphere, 700 ° C) after conditioning An alloy plating layer was formed on both surfaces by the following methods A to D, using the plating baths a to c shown in Table 1 on the steel sheet subjected to quality rolling (elongation rate 1.5%).
A: After alkaline electrolytic degreasing of the cold-rolled steel sheet and Ni plating using the plating bath a, annealing was performed at 700 ° C in a 10% H 2 + 90% N 2 atmosphere to diffuse and infiltrate the Ni plating. Then, after temper rolling with an elongation 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 tin were performed.
B: After annealing and temper rolling of cold-rolled steel sheet, alkaline electrolytic degreasing, sulfuric acid pickling, Ni plating treatment using plating bath a, and Sn plating treatment using plating bath c Then, a heat-melting treatment was performed in which the heat was maintained above the melting point of tin.
C: Cold-rolled steel sheet was annealed and temper-rolled, then alkaline electrolytically degreased, washed with sulfuric acid, Sn-plated using plating bath b, and heat-melted to heat and hold above the melting point of tin .
D: After annealing and temper rolling of the cold-rolled steel sheet, alkaline electrolytic degreasing, sulfuric acid pickling, then Sn plating treatment using the plating bath b, and heat melting treatment to heat and hold above the melting point of tin, Subsequently, cathodic electrolysis was performed in a 10 g / l aqueous sodium bicarbonate solution with a current of 5 A / dm 2 .
こうした合金めっき層を形成後、表2に示すZrおよびOを含有する皮膜形成処理浴Z1〜Z4を用い、表3に示す条件でZrおよびOを含有する皮膜を両面に形成させ、本発明例である表面処理鋼板No.1〜12を作製した。陰極電解処理の際は、陽極には酸化イリジウム皮膜したTiを用いた。ここで、表面処理鋼板No.2と3では、陰極電解処理ではなく浸漬処理によりZrおよびOを含有する皮膜が鋼板の両面に形成されている。 After forming such an alloy plating layer, a film containing Zr and O containing Zr and O shown in Table 2 was formed on both sides under the conditions shown in Table 3 using the Zr and O containing film forming treatment baths Z1 to Z4. Surface-treated steel sheets No. 1 to 12 were produced. In the cathode electrolysis treatment, Ti with an iridium oxide film was used for the anode. Here, in the surface-treated steel sheets No. 2 and 3, the coatings containing Zr and O are formed on both surfaces of the steel sheet not by cathodic electrolytic treatment but by immersion treatment.
また、比較例として、冷延鋼板を焼鈍後調質圧延した後、アルカリ電解脱脂し、硫酸酸洗後合金めっき層を形成せずにZrおよびOを含有する皮膜のみを形成させた表面処理鋼板No.13、14、上記Bの方法で非合金化Sn量が本発明範囲を超えた合金めっき層を形成後、表2のZ4浴を用いて表3に示す条件でZrおよびOを含有する皮膜を形成させた表面処理鋼板No.15、冷延鋼板を焼鈍後調質圧延した後、合金めっき層もZrおよびOを含有する皮膜も形成せず、リン酸Zn皮膜のみを形成させた表面処理鋼板No.16を作製した。 In addition, as a comparative example, a surface-treated steel sheet in which only a film containing Zr and O is formed without forming an alloy plating layer after alkaline electrolytic degreasing and after sulfuric acid pickling after temper rolling after annealing a cold-rolled steel sheet After forming an alloy plating layer in which the amount of non-alloyed Sn exceeded the scope of the present invention by the method of No. 13, 14 and B, Zr and O were contained under the conditions shown in Table 3 using the Z4 bath of Table 2 Surface-treated steel sheet No. 15 with a film formed on it, surface of cold-rolled steel sheet annealed after temper rolling, alloy plating layer and film containing Zr and O, only Zn phosphate film formed A treated steel plate No. 16 was produced.
そして、上記の方法で、合金めっき層のSn量、非合金化Sn量、ZrおよびOを含有する皮膜のZr量を測定し、Oの存在をXPSで確認するとともに、以下の方法で、合金めっき層のNi量、リン酸Zn皮膜の付着量の測定や、塗料密着性、ラミネートフィルム密着性(樹脂密着性)、耐錆性、耐食性の評価を行った。
合金めっき層中のNi量、リン酸Zn皮膜の付着量：蛍光Ｘ線分析により、予め付着量既知のサンプルを測定して得た検量線を用いて、求めた。
塗料密着性(Tピール試験)：2枚の表面処理鋼板試料表面にそれぞれエポキシ・フェノール系塗料を50mg/dm2となるように塗装し、鋼板温度210℃で10min焼付けた後、塗装面同士をナイロンフィルムを挟んで向かい合わせにしてホットプレスにて圧着し、これを5mm幅の試験片に分割し引張試験片を作成し、引張試験機を用いて向かい合わせ接着された鋼板の接着強度を測定し、次のように塗料密着性を評価した。ここで、◎、○であれば塗料密着性が良好であるとした。
◎：接着強度が2.5kg/5mm以上
○：接着強度が1.5kg/5mm以上2.5kg/5mm未満
△：接着強度が1kg/5mm以上1.5kg/5mm未満
×：接着強度が1kg/5mm未満
ラミネートフィルム密着性(180°ピール試験)：表面処理鋼板試料の両面に、厚さ25μm、共重合比12mol%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(有機樹脂被覆層)をラミネートして、ラミネート鋼板(樹脂被覆鋼板)を作製した。ラミネートは、245℃に加熱した金属板とフィルムを一対のゴムロールで挟んでフィルムを鋼板に融着させ、ゴムロール通過後1sec以内に水冷して行った。このとき、鋼板の送り速度は40m/min、ゴムロールのニップ長は17mmであった。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、図1の(a)に示すようなフィルム2を残して鋼板1の一部3を切リ取った試験片(サイズ：30mm×100mm)を用い、温度130℃、相対湿度100%のレトルト雰囲気中で、図1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、図1の(c)に示すフィルムの剥離長5を測定し、次のようにフィルム密着性を評価した。ここで、◎、○であればラミネートフィルム密着性が良好であるとした。
◎：フィルムの剥離長が20mm未満
○：フィルムの剥離長が20mm以上30未満
△：フィルムの剥離長が30mm以上70mm未満
×：フィルムの剥離長が70mm以上
耐錆性：端面および裏面をシールした表面処理鋼板試料(100mm×100mm)を温度60℃、相対湿度70%の雰囲気中に2週間放置し、錆発生個数をカウントし、次のように耐錆性を評価した。ここで、◎、○であれば耐錆性が良好であるとした。
◎：錆発生個数が0
○：錆発生個数が1〜10
△：錆発生個数が11〜50
×：錆発生個数が51以上
耐食性(UCC試験)：表面処理鋼板試料表面にそれぞれエポキシ・フェノール系塗料を50mg/dm2となるように塗装し、鋼板温度210℃で10min焼付けた後、4cm×8cmのサイズに切り出し、裏面と端面をシールした後、塗装面にカッターで地鉄に達するまでのカット(4cm長さ)を2本入れ(クロスカット)、1.5mass%NaCl水溶液と1.5mass%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4日間放置後、塗膜剥離(または腐食)の最大幅を測定し、次のように耐食性を評価した。ここで、◎、○であれば耐食性が良好であるとした。
◎：最大幅が0.2mm以下
○：最大幅が0.2mm超0.3mm以下
△：最大幅が0.3mm超0.5mm以下
×：最大幅が0.5mm超
結果を表4に示した。本発明例である表面処理鋼板No.１〜12は、塗料密着性、ラミネートフィルム密着性、耐錆性、耐食性に優れ、従来缶用素材として使用されているTFSと同等以上の特性を有している。
And by the above method, the Sn amount of the alloy plating layer, the non-alloyed Sn amount, the Zr amount of the coating containing Zr and O are measured, and the presence of O is confirmed by XPS. The amount of Ni in the plating layer and the amount of Zn phosphate coating deposited were measured, and paint adhesion, laminate film adhesion (resin adhesion), rust resistance, and corrosion resistance were evaluated.
The amount of Ni in the alloy plating layer and the amount of Zn phosphate coating deposited: The amount of Ni was determined using a calibration curve obtained by measuring a sample with a known amount deposited beforehand by fluorescent X-ray analysis.
Paint adhesion (T peel test): Two surface-treated steel sheet samples were each coated with an epoxy / phenolic paint at 50 mg / dm 2 and baked at a steel sheet temperature of 210 ° C for 10 min. Face each other with a nylon film and press-bond with a hot press, divide this into 5 mm wide test pieces, create a tensile test piece, and measure the adhesive strength of the steel sheets bonded face to face using a tensile tester The paint adhesion was evaluated as follows. Here, ◎ and ○ indicate that the paint adhesion is good.
◎: Adhesive strength 2.5kg / 5mm or more ○: Adhesive strength 1.5kg / 5mm or more, less than 2.5kg / 5mm △: Adhesive strength 1kg / 5mm or more, less than 1.5kg / 5mm ×: Laminate film with adhesive strength less than 1kg / 5mm Adhesiveness (180 ° peel test): Laminated steel sheet (resin) by laminating an isophthalic acid copolymerized polyethylene terephthalate film (organic resin coating layer) with a thickness of 25 μm and a copolymerization ratio of 12 mol% on both sides of the surface-treated steel sheet sample Coated steel sheet) was produced. Lamination was performed by sandwiching a metal plate heated to 245 ° C. and a film between a pair of rubber rolls, fusing the film to a steel plate, and cooling with water within 1 second after passing through the rubber roll. At this time, the feeding speed of the steel plate was 40 m / min, and the nip length of the rubber roll was 17 mm. Here, the nip length is the length in the conveyance direction of the portion where the rubber roll and the steel plate are in contact. Then, using a test piece (size: 30 mm × 100 mm) from which a part 3 of the steel plate 1 was cut out while leaving the film 2 as shown in FIG. 1 (a), a retort having a temperature of 130 ° C. and a relative humidity of 100% In the atmosphere, as shown in Fig. 1 (b), attach a weight 4 (100 g) to one end of the test piece, turn it back to 180 ° C on the film 2 side, and leave it for 30 min.The film shown in Fig. 1 (c) The peel length 5 was measured and the film adhesion was evaluated as follows. Here, if it is (double-circle) and (circle), the laminate film adhesiveness was said to be favorable.
◎: Film peel length is less than 20 mm ○: Film peel length is 20 mm or more and less than 30 △: Film peel length is 30 mm or more but less than 70 mm ×: Film peel length is 70 mm or more Rust resistance: Sealed end face and back face A surface-treated steel sheet sample (100 mm × 100 mm) was left in an atmosphere at a temperature of 60 ° C. and a relative humidity of 70% for 2 weeks, the number of rust occurrences was counted, and the rust resistance was evaluated as follows. Here, ◎ and ○ indicate that the rust resistance is good.
◎: No rust generation
○: Number of rust generation is 1 to 10
Δ: Number of rust generation is 11-50
×: Corrosion resistance of 51 or more rust generation (UCC test): Epoxy / phenolic paint was applied to the surface of each surface-treated steel sheet sample to 50 mg / dm 2 and baked for 10 min at a steel sheet temperature of 210 ° C, then 4 cm Cut to 8cm size, seal the back and end faces, put two cuts (4cm length) until reaching the iron core with a cutter on the painted surface (cross cut), 1.5mass% NaCl aqueous solution and 1.5mass% quencher The sample was immersed in 80 ml of a test solution in which the same amount of the acid aqueous solution was mixed and allowed to stand at 55 ° C. for 4 days. Then, the maximum width of coating film peeling (or corrosion) was measured, and the corrosion resistance was evaluated as follows. Here, ◎ and ○ indicate that the corrosion resistance is good.
◎: Maximum width is 0.2 mm or less ○: Maximum width is more than 0.2 mm and 0.3 mm or less △: Maximum width is more than 0.3 mm and 0.5 mm or less ×: Maximum width is more than 0.5 mm Table 4 shows the results. The surface-treated steel sheets No. 1 to 12, which are examples of the present invention, are excellent in paint adhesion, laminate film adhesion, rust resistance, corrosion resistance, and have characteristics equivalent to or better than TFS that has been used as a conventional can material. ing.
一方、比較例である合金めっき層を形成せずにZrおよびOを含有する皮膜のみを形成させた表面処理鋼板No.13は、耐錆性に劣っており、特に耐食性に著しく劣っている。同様に、合金めっき層を形成せずにZrおよびOを含有する皮膜のみを形成させた表面処理鋼板No.14は、ラミネートフィルム密着性、耐錆性および耐食性に劣っている。合金めっき層もZrおよびOを含有する皮膜も形成せず、リン酸Zn皮膜のみを形成させた表面処理鋼板No.16は、ラミネートフィルム密着性、耐錆性および耐食性に著しく劣っている。合金めっき層とZrおよびOを含有する皮膜を形成させた表面処理鋼板No.15は、耐錆性と耐食性には良好であるが、非合金化Sn量が多いためにラミネートフィルム密着性が著しく劣っている。 On the other hand, the surface-treated steel sheet No. 13 in which only the coating containing Zr and O is formed without forming the alloy plating layer as a comparative example is inferior in rust resistance, and particularly inferior in corrosion resistance. Similarly, surface-treated steel sheet No. 14 in which only a film containing Zr and O is formed without forming an alloy plating layer is inferior in laminate film adhesion, rust resistance, and corrosion resistance. Surface-treated steel sheet No. 16 in which neither an alloy plating layer nor a film containing Zr and O is formed and only a Zn phosphate film is formed is extremely inferior in laminate film adhesion, rust resistance and corrosion resistance. Surface-treated steel sheet No. 15 with an alloy plating layer and a film containing Zr and O is excellent in rust resistance and corrosion resistance, but due to the large amount of non-alloyed Sn, adhesion to the laminate film is remarkable. Inferior.
実施例1でラミネートフィルム密着性を調べるために作製された有機樹脂被覆層のラミネートされた表面処理鋼板No.1、4、6、9、11、16を用いて、表5に示す条件で製缶加工を行い、缶胴の開口端をネックイン、フランジ加工して金属シームレス缶No.1〜6を作製した。また、同じ樹脂被覆鋼板を用いて、209径のSOT蓋を作製し、スコア加工部内外面をエポキシフェノール系塗料で補修した。 Using the surface-treated steel sheets No. 1, 4, 6, 9, 11, and 16 laminated with the organic resin coating layer prepared for examining the adhesion of the laminate film in Example 1, the conditions shown in Table 5 were used. Can processing was carried out, and metal cans No. 1 to 6 were produced by necking in and opening the opening end of the can body. In addition, using the same resin-coated steel plate, a 209-diameter SOT lid was prepared, and the inner and outer surfaces of the score processed part were repaired with an epoxy phenol-based paint.
作製した缶No.1〜6および蓋について、製缶後のフィルムの剥離や穴あきなどの異常の有無を目視で調査した。また、50℃でコーヒー飲料を充填した後、蓋を2重巻締めし、125℃で25min間のレトルト処理を行い、37℃で6ヶ月放置後開缶して、缶内面側の腐食やフィルム異常を目視で調査した。 The produced cans Nos. 1 to 6 and the lids were visually inspected for abnormalities such as film peeling and perforation after canning. After filling the coffee beverage at 50 ° C, double-wrap the lid, perform retort treatment at 125 ° C for 25 min, leave it at 37 ° C for 6 months, and then open the can. Abnormalities were examined visually.
結果を表6に示す。本発明である樹脂被覆鋼板と表面処理鋼板を用いた缶No.1〜5には、製缶後および内容物充填後、缶および蓋を調べたが、いずれにおいてもフィルムの異常は確認されなかった。 The results are shown in Table 6. For cans No. 1 to 5 using the resin-coated steel sheet and the surface-treated steel sheet according to the present invention, the can and the lid were inspected after making the can and after filling the contents, but no abnormality of the film was confirmed in any case It was.
一方、本発明でない樹脂被覆鋼板を用いた缶No.6は、製缶後および内容物充填後にフィルム異常や、内容物充填後に腐食が確認された。 On the other hand, can No. 6 using a resin-coated steel sheet not according to the present invention was confirmed to have a film abnormality after corrosion and after filling the contents and after the contents were filled.
1 鋼板
2 フィルム
3 鋼板の切リ取った部位
4 重り
5 剥離長
1 Steel plate
2 film
3 Parts removed from the steel plate
4 weights
5 Peel length
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| JP4774629B2 (en) * | 2001-05-18 | 2011-09-14 | Ｊｆｅスチール株式会社 | Polyester resin coated tin alloy plated steel sheet |
| JP4492103B2 (en) * | 2002-11-25 | 2010-06-30 | 東洋製罐株式会社 | Surface-treated metal material and surface treatment method thereof, resin-coated metal material, metal can, can lid |
| JP3944129B2 (en) * | 2003-07-07 | 2007-07-11 | 新日本製鐵株式会社 | Surface-treated steel sheet for containers with excellent weldability, corrosion resistance, and paint adhesion |
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2005
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