JP5326379B2 - Surface-treated steel sheet and resin-coated steel sheet - Google Patents
Surface-treated steel sheet and resin-coated steel sheet Download PDFInfo
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- JP5326379B2 JP5326379B2 JP2008168071A JP2008168071A JP5326379B2 JP 5326379 B2 JP5326379 B2 JP 5326379B2 JP 2008168071 A JP2008168071 A JP 2008168071A JP 2008168071 A JP2008168071 A JP 2008168071A JP 5326379 B2 JP5326379 B2 JP 5326379B2
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- 229920005989 resin Polymers 0.000 title claims description 99
- 239000011347 resin Substances 0.000 title claims description 99
- 229910000831 Steel Inorganic materials 0.000 title claims description 75
- 239000010959 steel Substances 0.000 title claims description 75
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 238000001878 scanning electron micrograph Methods 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 description 52
- 239000002313 adhesive film Substances 0.000 description 37
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000005029 tin-free steel Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- -1 potassium fluorinated titanate Chemical class 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910000576 Laminated steel Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002335 surface treatment layer Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000004141 dimensional analysis Methods 0.000 description 4
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 238000007765 extrusion coating Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical class F* 0.000 description 2
- 238000007654 immersion 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
- 239000007769 metal material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000001263 FEMA 3042 Substances 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
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 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 1
- 238000001816 cooling Methods 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
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology 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
- 238000001198 high resolution scanning electron microscopy 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
- 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
- 238000004898 kneading Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 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
- 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
- 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
- 238000001420 photoelectron spectroscopy Methods 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
- 229920000728 polyester 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
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 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
- 239000002356 single layer Substances 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
- 239000000126 substance Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (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が被覆された後、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)に優れる表面処理鋼板、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 the resin is coated by laminating a resin film or the like on the surface or coating a resin-containing paint, particularly in a high temperature and humid environment. The present invention relates to a surface-treated steel sheet having excellent adhesion to a coated resin (hereinafter referred to as wet resin adhesion), and a resin-coated steel sheet in which the surface-treated steel sheet is coated with a resin.
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、塗料など樹脂との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 have a feature of having 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。例えば、特許文献1には、タングステン酸溶液中で電解処理が施された容器用鋼板が開示されている。また、特許文献2には、表面にリン酸塩層が形成された容器用表面処理鋼板が開示されている。さらに、特許文献3には、Sn、Niの1種以上を含む表面処理層の上にタンニン酸または酢酸の1種以上およびTiまたはZrまたはそれらの化合物の1種以上を含んだフェノール構造を有する樹脂皮膜が形成された容器用鋼板が提案されている。さらにまた、特許文献4には、リン酸イオンを含有しない、Ti、O、Fを主成分とする無機表面処理層と有機表面処理層が形成されている表面処理金属材料が提案されている。 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. For example, Patent Document 1 discloses a steel plate for containers that has been subjected to electrolytic treatment in a tungstic acid solution. Patent Document 2 discloses a surface-treated steel sheet for containers having a phosphate layer formed on the surface. Furthermore, Patent Document 3 has a phenol structure containing one or more of tannic acid or acetic acid and one or more of Ti or Zr or a compound thereof on a surface treatment layer containing one or more of Sn and Ni. A steel plate for containers in which a resin film is formed has been proposed. Furthermore, Patent Document 4 proposes a surface-treated metal material that does not contain phosphate ions and has an inorganic surface treatment layer and an organic surface treatment layer mainly composed of Ti, O, and F.
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、塗装に代わって樹脂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強い湿潤樹脂密着性が要求される。
しかしながら、特許文献1に記載のタングステン酸溶液中で電解処理が施された容器用鋼板、特許文献2に記載の表面にリン酸塩層が形成された容器用表面処理鋼板を用いた樹脂被覆鋼板、特許文献3に記載のフェノール構造を有する樹脂皮膜が形成された容器用鋼板および特許文献4に記載のTi、O、Fを主成分とする無機表面処理層と有機表面処理層が形成されている表面処理金属材料では、いずれもレトルト雰囲気における湿潤樹脂密着性が不十分である。 However, a resin-coated steel sheet using a container steel plate subjected to electrolytic treatment in a tungstic acid solution described in Patent Document 1, and a container surface-treated steel sheet having a phosphate layer formed on the surface described in Patent Document 2 The steel sheet for containers in which the resin film having a phenol structure described in Patent Document 3 is formed, and the inorganic surface treatment layer and the organic surface treatment layer mainly composed of Ti, O, and F described in Patent Document 4 are formed. In any of the surface-treated metal materials, the wet resin adhesion in the retort atmosphere is insufficient.
本発明は、Crを用いず、湿潤樹脂密着性に優れ、ティンフリー鋼板の代替材となり得る表面処理鋼板、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を提供することを目的とする。 An object of the present invention is to provide a surface-treated steel sheet that does not use Cr, has excellent wet resin adhesion, and can be used as a substitute for a tin-free steel sheet, and a resin-coated steel sheet in which a resin is coated on the surface-treated steel sheet. .
本発明者らは、Crを用いず、湿潤樹脂密着性に優れ、ティンフリー鋼板の代替材となり得る表面処理鋼板について鋭意研究を重ねた結果、鋼板表面に、Tiを含み、多数の微細な凸部を均一に有する湿潤樹脂密着性に優れた皮膜(以下、密着性皮膜と略す場合がある。)を形成することにより極めて優れた湿潤樹脂密着性が得られることを見出した。 As a result of intensive research on a surface-treated steel sheet that does not use Cr, has excellent wet resin adhesion, and can be used as a substitute for a tin-free steel sheet, the surface of the steel sheet contains Ti and contains a large number of fine protrusions. It has been found that extremely excellent wet resin adhesion can be obtained by forming a film having a uniform part and excellent wet resin adhesion (hereinafter sometimes abbreviated as an adhesive film ) .
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、Ti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種の金属イオンを含有する水溶液中で鋼板を陰極電解処理して得た、厚さが20〜800nmのTiを含む湿潤樹脂密着性に優れた皮膜を有し、かつ該湿潤樹脂密着性に優れた皮膜には、1個/μm以上の線密度で凸部が存在し、かつ、前記湿潤樹脂密着性に優れた皮膜に含有されるTiに対するCo、Fe、Ni、V、Cu、MnおよびZnの質量比が0.01〜10であることを特徴とする表面処理鋼板を提供する。ここで、湿潤樹脂密着性に優れた皮膜の厚さとは、透過電子顕微鏡(TEM)で観察した皮膜断面プロファイルにおいて、皮膜下面から測定した凸部の最大高さHのことであり、湿潤樹脂密着性に優れた皮膜の凸部の線密度とは、凹部の底の皮膜下面からの最小高さをLとし、(H+L)/2の位置を中心にして±10nmの上下レベルの水平線を引いたとき、下レベルの水平線と断面プロファイルの曲線が交差する隣接の2点間において、上レベルの水平線とプロファイルの曲線が交差する点が1回以上存在する場合に1個の凸部が存在するとして求めた凸部の単位長さあたりの個数のことである。 The present invention has been made based on such knowledge, and includes at least one metal selected from Co, Fe, Ni, V, Cu, Mn, and Zn, including Ti on at least one side of the steel sheet. the steel sheet in an aqueous solution containing the ions obtained by cathodic electrolytic treatment has a film excellent wet resin adhesion, including thickness of Ti 20 to 800 nm, and the film excellent in the wet resin adhesion Is a mass ratio of Co, Fe, Ni, V, Cu, Mn and Zn to Ti contained in the film having a linear density of 1 piece / μm or more and having excellent wet resin adhesion Is a surface-treated steel sheet, characterized by being 0.01 to 10 . Here, the thickness of the film excellent wet resin adhesion, the coating section profile observed with a transmission electron microscope (TEM), and that the maximum height H of the projection measured from the film lower surface, wet resin adhesion The line density of the convex part of the film with excellent properties is the minimum height from the lower surface of the film at the bottom of the concave part, and the horizontal line at the upper and lower levels of ± 10 nm centered on the position of (H + L) / 2 When it is drawn, there is one convex part when there is at least one point where the upper level horizontal line intersects the profile curve between two adjacent points where the lower level horizontal line intersects the profile profile curve. This is the number of convex portions per unit length obtained as if.
また、本発明の表面処理鋼板では、走査電子顕微鏡(SEM)で観察した密着性皮膜表面のSEM像を3次元解析することにより、密着性皮膜に存在する凸部の分布状態を16個/μm2以上の面密度で定義することもできる。ここで、密着性皮膜の凸部の面密度とは、SEMで観察した皮膜表面のSEM像を3次元解析し、1.0μmのカットオフ波長でフィルター処理を施して求めた凹凸の平均線+0.005μm以上の高さを有する凸部の単位面積あたり個数のことである。 Further, in the surface-treated steel sheet of the present invention, the distribution state of the convex portions existing in the adhesive film is 16 / μm by three-dimensionally analyzing the SEM image of the surface of the adhesive film observed with a scanning electron microscope (SEM). It can also be defined by an area density of 2 or more. Here, the surface density of the convex part of the adhesive film is the average line of the unevenness obtained by performing a three-dimensional analysis of the SEM image of the film surface observed by SEM and filtering at a cutoff wavelength of 1.0 μm + 0.005 It is the number of convex portions having a height of μm or more per unit area.
本発明の表面処理鋼板では、SEMによる3次元データから断面曲線を抜き出して、1.0μmのカットオフ波長でフィルター処理後求めたJIS B 0601:2001に規定される二乗平均平方根粗さ(Rq)と算術平均粗さ(Ra)との比(Rq/Ra)が1.3以下であることが好ましい。また、SEMによる3次元データから断面曲線を抜き出して、1.0μmのカットオフ波長でフィルター処理後求めたJIS B 0601:2001に規定されるスキューネス(Rsk)が0.6以下、またはクルトシス(Rku)が4以下であることがより好ましい。 In the surface-treated steel sheet of the present invention, the cross-sectional curve is extracted from the three-dimensional data by SEM, and the root mean square roughness (Rq) defined in JIS B 0601: 2001 obtained after filtering with a cutoff wavelength of 1.0 μm and The ratio (Rq / Ra) to the arithmetic average roughness (Ra) is preferably 1.3 or less. In addition, the cross-sectional curve is extracted from the three-dimensional data by SEM, and the skewness (Rsk) specified in JIS B 0601: 2001 obtained after filtering at a cutoff wavelength of 1.0 μm is 0.6 or less, or the kurtosis (Rku) is 4 The following is more preferable.
本発明の表面処理鋼板では、密着性皮膜のTi量が片面あたり3〜200mg/m2であることが好ましい。 In the surface-treated steel sheet of the present invention, the Ti amount of the adhesive film is preferably 3 to 200 mg / m 2 per side.
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ことを特徴とする樹脂被覆鋼板を提供する。 The present invention also provides a resin-coated steel sheet, wherein 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、湿潤樹脂密着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、樹脂の剥離が全く生じない。 According to the present invention, it has become possible to produce a surface-treated steel sheet having excellent wet resin adhesion 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 at all.
1)表面処理鋼板
上述したように、本発明の表面処理鋼板では、鋼板の少なくとも片面に、厚さが20〜800nmのTiを含み、かつ1個/μm以上の線密度で凸部が存在する密着性皮膜、あるいは16個/μm2以上の面密度で凸部が存在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る。以下に、その詳細を説明する。
1) Surface-treated steel sheet As described above, in the surface-treated steel sheet of the present invention, at least one side of the steel sheet contains Ti having a thickness of 20 to 800 nm and has convex portions with a linear density of 1 piece / μm or more. Excellent wet resin adhesion can be obtained by forming an adhesive film or an adhesive film having convex portions with an area density of 16 / μm 2 or more. The details will be described below.
素材の鋼板としては、低炭素鋼や極低炭素鋼などの一般的な缶用の鋼板を用いることができる。 As the raw steel plate, a general steel plate for cans such as low carbon steel and extremely low carbon steel can be used.
鋼板表面にTiを含んだ密着性皮膜を形成させると湿潤樹脂密着性が向上する理由は、現在のところ必ずしも明確ではないが、Tiの酸化物を主体とした高分子量の皮膜が、樹脂との間に強い分子間力を発生するためであると推測される。したがって、密着性皮膜にはOを含有させることが好ましい。 The reason why the wet resin adhesion improves when an adhesive film containing Ti is formed on the steel sheet surface is not necessarily clear at present, but a high molecular weight film mainly composed of an oxide of Ti is not compatible with the resin. It is assumed that this is because a strong intermolecular force is generated between them. Therefore, it is preferable to contain O in the adhesive film.
密着性皮膜のTi量は、片面あたり3〜200mg/m2であることが好ましい。これは、Ti量が3mg/m2以上でより優れた湿潤樹脂密着性が得られ、200mg/m2を超えるとその効果が飽和する傾向にあるためである。なお、密着性皮膜のTi量の測定は、蛍光X線分析法により行うことができる。また、O量については、特に規定しないが、光電子分光法(XPS)によりその存在を確認することができる。 The amount of Ti in the adhesive film is preferably 3 to 200 mg / m 2 per side. This is because better wet resin adhesion can be obtained when the Ti content is 3 mg / m 2 or more, and the effect tends to be saturated when it exceeds 200 mg / m 2 . Note that the Ti amount of the adhesive film can be measured by fluorescent X-ray analysis. The amount of O is not particularly defined, but its presence can be confirmed by photoelectron spectroscopy (XPS).
また、密着性皮膜の厚さを20〜800nmとする理由は、厚さが20nm未満では優れた湿潤樹脂密着性が得られず、800nmを超えると皮膜自体が脆くなり湿潤樹脂密着性が劣化するためである。 Also, the reason why the thickness of the adhesive film is 20 to 800 nm is that if the thickness is less than 20 nm, excellent wet resin adhesion cannot be obtained, and if it exceeds 800 nm, the film itself becomes brittle and the wet resin adhesion deteriorates. Because.
さらに、密着性皮膜に1個/μm以上の線密度で凸部を存在させると湿潤樹脂密着性が向上する理由は、次のように考えられる。すなわち、図1に本発明である表面処理鋼板の密着性皮膜断面を模式的に示したが、このように凸部を均一で密に存在させる、具体的には1個/μm以上の線密度で存在させると、図2に模式的に示したような比較例である表面処理鋼板の不均一で疎な凸部が存在する皮膜に比べ、表面積が増大して樹脂との接着面積が増加するとともに、均一で密に存在する凹凸部によるアンカー効果が増大して極めて優れた湿潤樹脂密着性が得られる。一方、こうした凸部の線密度が1個/μm未満だと、樹脂との接着面積が減少するとともに、アンカー効果が十分でなくなり、上記のような効果が発揮されず優れた湿潤樹脂密着性が得られない。 Furthermore, the reason why the wet resin adhesion is improved when a convex portion is present at a linear density of 1 piece / μm or more in the adhesive film is considered as follows. That is, FIG. 1 schematically shows a cross section of the adhesive film of the surface-treated steel sheet according to the present invention. In this way, the convex portions are present uniformly and densely, specifically, a linear density of 1 piece / μm or more. In the case of being present, the surface area is increased and the adhesion area with the resin is increased as compared with a film having uneven and sparse convex portions of the surface-treated steel sheet which is a comparative example as schematically shown in FIG. At the same time, the anchor effect by the uneven portions present uniformly and densely increases, and extremely excellent wet resin adhesion can be obtained. On the other hand, if the linear density of these convex portions is less than 1 piece / μm, the area of adhesion with the resin is reduced, the anchor effect is not sufficient, and the above effect is not exhibited and excellent wet resin adhesion is achieved. I can't get it.
ここで、密着性皮膜の厚さや密着性皮膜の凸部の線密度は以下のよう定義される。このとき、皮膜面内の任意の方向で観察した皮膜断面プロファイルを用いることができる。 Here, the thickness of the adhesive film and the linear density of the convex part of the adhesive film are defined as follows. At this time, a film cross-sectional profile observed in an arbitrary direction within the film surface can be used.
図3に、本発明である表面処理鋼板の密着性皮膜の厚さ、凸部の線密度を説明するための模式図を示す。密着性皮膜の厚さとは、TEMで観察した皮膜断面プロファイルにおいて、皮膜下面から測定した凸部の最大高さHのことであり、密着性皮膜の凸部の線密度とは、凹部の底の皮膜下面からの最小高さをLとし、(H+L)/2の位置を中心にして±10nmの上下レベルの水平線を引いたとき、下レベルの水平線と断面プロファイルの曲線が交差する2点間において、上レベルの水平線とプロファイルの曲線が交差する点が1回以上存在する場合に1個の凸部が存在するとして求めた凸部の単位長さあたりの個数のことである。 FIG. 3 is a schematic diagram for explaining the thickness of the adhesive film of the surface-treated steel sheet according to the present invention and the linear density of the convex portions. The thickness of the adhesive film is the maximum height H of the convex part measured from the lower surface of the film cross-sectional profile observed with TEM. The linear density of the convex part of the adhesive film is the bottom of the concave part. Two points where the horizontal line of the lower level intersects the curve of the cross-sectional profile when the horizontal line of the upper and lower levels of ± 10nm is drawn centering on the position of (H + L) / 2, where L is the minimum height from the lower surface of the film This is the number of convex portions per unit length obtained by assuming that one convex portion exists when there is a point where the upper level horizontal line intersects with the profile curve at least once.
密着性皮膜の厚さHを測定するには、TEMで観察した皮膜断面プロファイルから最も高い凸部を選び、皮膜下面から測定したその高さを求めればよい。一方、凹部の底の皮膜下面からの最小高さLを測定するには、観察している皮膜断面プロファイルから最も低い凹部の底を選び、皮膜下面から測定したその高さを求めればよい。 In order to measure the thickness H of the adhesive film, the highest convex portion is selected from the film cross-sectional profile observed with TEM, and the height measured from the lower surface of the film is obtained. On the other hand, in order to measure the minimum height L of the bottom of the recess from the lower surface of the film, the lowest bottom of the recess is selected from the observed cross-sectional profile of the film, and the height measured from the lower surface of the film is obtained.
本発明では、SEMで観察した密着性皮膜表面のSEM像を3次元解析することにより、密着性皮膜に存在する凸部の分布状態を16個/μm2以上の面密度で定義することもできる。図4に、本発明例(後述する実施例のNo.2)および比較例(後述する比較例のNo.1)のSEM像を示したが、本発明例(a)では、比較例(b)の場合に比べ、皮膜の凸部が均一で密に存在していることがわかる。上述したように、均一で密な凸部の存在により表面積が増大して樹脂との接着面積が増加するとともに、凹凸部によるアンカー効果が増大して極めて優れた湿潤樹脂密着性が得られると考えられる。 In the present invention, the three-dimensional analysis of the SEM image of the surface of the adhesive film observed with the SEM can define the distribution state of the convex portions existing in the adhesive film with an area density of 16 pieces / μm 2 or more. . FIG. 4 shows SEM images of an example of the present invention (No. 2 of an example described later) and a comparative example (No. 1 of a comparative example described later). In the example of the present invention (a), a comparative example (b ), It can be seen that the convex portions of the film are uniform and dense. As described above, the presence of uniform and dense convex portions increases the surface area and increases the adhesion area with the resin, and the anchor effect by the concave and convex portions is increased to provide extremely excellent wet resin adhesion. It is done.
ここで、密着性皮膜の凸部の面密度は、図4に示したSEM像(6μm×4.5μmの領域)を3次元解析し、1.0μmのカットオフ波長でフィルター処理を施してうねり成分を除去して求めた凹凸の平均線+0.005μm以上の高さを有する凸部の単位面積あたり個数として求めることができる。 Here, the surface density of the convex part of the adhesive film is obtained by three-dimensional analysis of the SEM image (6 μm × 4.5 μm region) shown in FIG. The average line of unevenness obtained by removing + the number of convex parts having a height of 0.005 μm or more can be obtained per unit area.
密着性皮膜の凸部の密度を、TEMで観察した皮膜断面プロファイルから求めた線密度とSEMで観察した皮膜表面の像を3次元解析することにより求めた面密度とで別々に規定した理由は、前者では、密着性皮膜そのものを直接観察できるが、試料作製や測定に時間がかかるという問題があり、後者では、皮膜上に樹脂被覆層がある場合などは樹脂被覆層を除去するのに時間がかかるが、測定自体は簡便であり、迅速に行えるためである。なお、本発明では、線密度で規定した場合も面密度で規定した場合も、等価な湿潤樹脂密着性が得られることを確認している。 The reason why the density of the convex part of the adhesive film was separately defined by the line density obtained from the film cross-sectional profile observed with TEM and the surface density obtained by three-dimensional analysis of the film surface image observed with SEM is In the former case, the adhesive film itself can be observed directly, but there is a problem that it takes time to prepare and measure the sample. In the latter case, when there is a resin coating layer on the film, it takes time to remove the resin coating layer. However, the measurement itself is simple and can be performed quickly. In the present invention, it has been confirmed that equivalent wet resin adhesion can be obtained both when defined by linear density and when defined by surface density.
さらに、SEMによる3次元データから断面曲線を抜き出して、1.0μmのカットオフ波長でフィルター処理後求めたJIS B 0601:2001に規定されるRqとRaとの比(Rq/Ra)を1.3以下にすると、より均一で密な凸部分布が得られるので好ましい。また、同様に、SEMによる3次元データから断面曲線を抜き出して、1.0μmのカットオフ波長でフィルター処理後求めたJIS B 0601:2001に規定されるRskを0.6以下、またはRkuを4以下にすると、密着性皮膜上に樹脂を被覆する時に表面積が大きくなるだけではなく、強固な界面を作るために成形時の圧力に耐え、かつアンカー効果を発現できるのでより好ましい。 Furthermore, the cross-sectional curve is extracted from the three-dimensional data by SEM, and the ratio (Rq / Ra) of Rq and Ra specified in JIS B 0601: 2001 obtained after filtering at a cutoff wavelength of 1.0 μm (Rq / Ra) is 1.3 or less. Then, since a more uniform and dense convex part distribution is obtained, it is preferable. Similarly, when the cross-sectional curve is extracted from the three-dimensional data obtained by SEM, the Rsk specified in JIS B 0601: 2001 obtained after filtering at a cutoff wavelength of 1.0 μm is 0.6 or less, or the Rku is 4 or less. It is more preferable not only to increase the surface area when coating the resin on the adhesive film, but also to withstand the pressure at the time of molding in order to create a strong interface and to develop the anchor effect.
密着性皮膜の形成方法としては、Ti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種の金属イオンを含有する水溶液中で、鋼板を陰極電解処理または浸漬処理する方法が好ましい。Tiを含む水溶液としては、フルオロチタン酸イオンを含む水溶液、またはフルオロチタン酸イオンおよびフッ素塩を含む水溶液が好適である。フルオロチタン酸イオンを与える化合物としては、フッ化チタン酸、フッ化チタン酸アンモニウム、フッ化チタ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、フッ化チタン酸カリウムを含む水溶液中で、あるいはフッ化チタン酸カリウムおよびフッ化ナトリウムを含む水溶液中で、鋼板を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であり好適である。 As a method for forming an adhesive film, a steel plate is subjected to cathodic electrolysis in an aqueous solution containing Ti and further containing at least one metal ion selected from Co, Fe, Ni, V, Cu, Mn and Zn. A method of treating or dipping is preferred. As the aqueous solution containing Ti, an aqueous solution containing fluorotitanate ions or an aqueous solution containing fluorotitanate ions and a fluorine salt is suitable. As the compound that gives fluorotitanate ions, fluorinated titanate, ammonium fluoride titanate, potassium fluoride titanate, and the like can be used. As the fluorine salt, sodium fluoride, potassium fluoride, silver fluoride, tin fluoride, or the like can be used. In particular, the method of cathodic electrolysis of a steel sheet in an aqueous solution containing potassium fluorinated titanate or an aqueous solution containing potassium fluorinated titanate and sodium fluoride can form a uniform film efficiently. It is preferable.
また、Co、Fe、Ni、V、Cu、MnおよびZnイオン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。 The compounds that give Co, Fe, Ni, V, Cu, Mn and Zn ions include cobalt sulfate, cobalt chloride, iron sulfate, iron chloride, nickel sulfate, copper sulfate, vanadium oxide sulfate, zinc sulfate, manganese sulfate, etc. Can be used.
さらに、密着性皮膜のTiに対するこれら金属元素の質量比が0.01〜10となるように、前記水溶液中のTiイオンと金属イオンの質量比を調整すればよい。また、陰極電解処理における電流密度および電解時間、ならびに浸漬処理における浸漬時間は、必要なTi量に応じて適宜決定すればよい。これら金属元素の皮膜中の含有量は、前述したTEM観察においてエネルギー分散型X線分析法(EDX)あるいは電子線エネルギー損失分光法(EELS)により測定することができる。 Furthermore, what is necessary is just to adjust the mass ratio of Ti ion and metal ion in the said aqueous solution so that mass ratio of these metal elements with respect to Ti of an adhesive film may be set to 0.01-10. Moreover, what is necessary is just to determine suitably the current density and electrolysis time in cathodic electrolysis processing, and the immersion time in immersion treatment according to required Ti amount. The content of these metal elements in the film can be measured by energy dispersive X-ray analysis (EDX) or electron beam energy loss spectroscopy (EELS) in the TEM observation described above.
2)樹脂被覆鋼板
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 A resin-coated steel sheet can be obtained 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、ラミネート用の樹脂フィルムであっても、塗装用の樹脂塗料であってもよく、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。ラミネート用としては、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であってもよい。積層(ラミネート)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 resin coated on the surface-treated steel sheet of the present invention may be a resin film for lamination or a resin paint for coating, and is not particularly limited, and examples thereof include various thermoplastic resins and thermosetting resins. be able to. For laminating, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyester such as polybutylene terephthalate. It may be an unstretched or biaxially stretched film or a thermoplastic resin film such as nylon 6, nylon 6,6, nylon 11, nylon 12 or other polyamide film, polyvinyl chloride film, polyvinylidene chloride film, etc. . When using an adhesive during lamination (urethane), urethane adhesive, epoxy adhesive, acid-modified olefin resin adhesive, copolyamide adhesive, copolyester adhesive (thickness: 0.1-5.0 μm) and the like are 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、塗装用としては、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。 For coating, modified epoxy paints such as phenol epoxy and amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Thermoplastic or thermosetting paints such as coalesced, epoxy-modified, epoxy-amino-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 of two or more.
本発明において、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 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、表面処理鋼板への樹脂被覆層の形成は任意の手段で行うことができる。ラミネートにより樹脂被覆する場合は、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。 In the present invention, the resin coating layer can be formed on the surface-treated steel sheet by any means. When resin coating is performed by laminating, for example, extrusion coating, cast film thermal bonding, biaxially stretched film thermal bonding, or the like can be used. 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 melt-kneading the resin with an extruder, the resin is extruded from a T-die into a thin film, and the extruded molten resin film is pressed and integrated with a surface-treated steel sheet between a pair of laminate rolls, 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1に示す表面処理鋼板No.1〜8を作製する。 Cathodic electrolysis was performed on both sides of cold-rolled cold-rolled steel plate (thickness 0.2 mm) as cold-rolled steel used for the production of tin-free steel plates (TFS) under the conditions of cathodic electrolysis shown in Table 1. Then, an adhesive film is formed by drying, and surface-treated steel sheets Nos. 1 to 8 shown in Table 1 are produced.
そして、密着性皮膜のTi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。密着性皮膜中に検出される金属元素についてはXPS、オージェ電子分光法(AES)、グロー放電分光法(GDS)などの表面分析法の他、TEMに付属するEDXを併用して評価する。Feについては下地鋼板に含まれるため、極薄皮膜である本発明の密着性皮膜内に存在することの確認はEDXのみでは不十分と考え、TEMに付属するEELSによっても行う。また、Co、Fe、Ni、V、Cu、MnおよびZnの付着量についてはTiと同様の蛍光X線分析法、ならびに化学分析法、AESおよび二次イオン質量分析法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Tiに対するCo、Fe、Ni、V、Cu、MnおよびZnの質量比を求める。なお、Oは、No.1〜8のすべてについてXPSによりその存在を確認する。 The Ti amount of the adhesive film is obtained by fluorescent X-ray analysis in comparison with a calibration plate obtained by chemical analysis of the adhesion amount in advance. In addition to surface analysis methods such as XPS, Auger Electron Spectroscopy (AES), and Glow Discharge Spectroscopy (GDS), metal elements detected in adhesive films are evaluated using EDX attached to TEM. Since Fe is contained in the base steel sheet, it is considered that EDX alone is insufficient to confirm that it is present in the adhesive film of the present invention, which is an ultrathin film, and is also performed by EELS attached to the TEM. For the amount of Co, Fe, Ni, V, Cu, Mn, and Zn deposited, select the appropriate measurement method from the fluorescent X-ray analysis method similar to Ti, chemical analysis method, AES, and secondary ion mass spectrometry method. The mass ratio of Co, Fe, Ni, V, Cu, Mn and Zn to Ti contained in the adhesive film is obtained. In addition, O confirms the presence by XPS about all of No. 1-8.
密着性皮膜の厚さや凸部の線密度は、前述のように、皮膜断面をFIBにより加工して薄膜サンプルを作製し、TEM観察による断面プロファイルを基に測定する。このとき、予めSEM観察して評価部位を位置決め、保護皮膜を形成させた上でGaイオンを用いたFIBにより断面加工を行って約0.1μmの薄膜としてTEM観察を行う。なお、本発明ではFIBはSII-NT(株)製SMI-3050MS2、TEMは日本電子(株)製JEM-2010Fを用いる。 As described above, the thickness of the adhesive film and the linear density of the protrusions are measured based on the cross-sectional profile obtained by TEM observation by processing the film cross section with FIB to produce a thin film sample. At this time, SEM observation is performed in advance, the evaluation site is positioned, a protective film is formed, and then cross-section processing is performed by FIB using Ga ions to perform TEM observation as a thin film of about 0.1 μm. In the present invention, FIB uses SMI-3050MS2 manufactured by SII-NT, and TEM uses JEM-2010F manufactured by JEOL.
また、SEM像は、凹凸形状を測定できるSEMで取得する。本発明では、エリオニクス(株)製の高分解能SEM ERA-8800FEを用いる。この装置は、試料方向を向いた4本の二次電子検出器を備えており、二次電子の和信号や差信号から組成の違いを強調した像や特定方向の凹凸を反映した像を表示することができる。得られたSEM像をもとに、Rq、Ra、Rsk、Rkuは前記装置付属の画像処理ソフトを用いて算出する。凸部の面密度については前記装置で得たSEM像を、長岡技術大学柳研究室が開発した三次元表面形状解析ソフト「SUMMIT」を用いて算出する。このとき、試料は観察前にAuを約10nm蒸着し、加速電圧5kV、倍率20000倍でSEM像観察を行う。各試料とも任意の5箇所の視野で解析し、平均して凸部の面密度などを求める。なお、Rq、Ra、Rsk、Rkuを算出する際は、各視野につき断面曲線を100本以上抜き出し、それぞれについて抽出した粗さ曲線を評価した値を平均してそれぞれの視野の評価値とし、さらにそれを5視野で平均する。 In addition, the SEM image is acquired by an SEM that can measure the uneven shape. In the present invention, high resolution SEM ERA-8800FE manufactured by Elionix Co., Ltd. is used. This device is equipped with four secondary electron detectors facing the sample direction, and displays an image that emphasizes the difference in composition from the sum and difference signals of secondary electrons and an image that reflects irregularities in a specific direction. can do. Based on the obtained SEM image, Rq, Ra, Rsk and Rku are calculated using the image processing software attached to the apparatus. The surface density of the convex part is calculated using the SEM image obtained by the above apparatus using the three-dimensional surface shape analysis software “SUMMIT” developed by Nagaoka Institute of Technology Yanagi Laboratory. At this time, about 10 nm of Au is deposited on the sample before observation, and SEM image observation is performed at an acceleration voltage of 5 kV and a magnification of 20000 times. Analyze each sample from five arbitrary fields of view and average the surface density of the protrusions. When calculating Rq, Ra, Rsk, Rku, extract 100 or more cross-sectional curves for each visual field, average the values obtained by evaluating the roughness curves extracted for each, and obtain the evaluation value for each visual field. Average it over 5 fields of view.
また、これらの表面処理鋼板No.1〜8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.1〜8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.1〜8について、下記の湿潤樹脂密着性の評価を行う。
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5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5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5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10mm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。
In addition, on both surfaces of these surface-treated steel sheets No. 1 to 8, 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. Lamination conditions with a degree of axial orientation (BO value) of 150, that is, steel sheet feed speed: 40 m / min, rubber roll nip length: 17 mm, and time to water cooling after crimping: 1 second Make 1-8. 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. 1-8, the following wet resin adhesiveness evaluation is performed.
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 on the front and back sides set to n = 1, leaving a film 2 as shown in Fig. 5 (a) and cutting off part 3 of the steel plate 1 , N = 2 for each laminated steel plate), and as shown in Fig. 5 (b), attach a weight 4 (100g) to one end of the test piece and turn it 180 ° to the film 2 side and leave it for 30min. This is a film peeling test. Then, the peel length 5 shown in (c) of FIG. 5 is measured and evaluated, and the average of the peel lengths (n = 2) on the front and back surfaces of each laminated steel sheet is obtained. It can be said that the smaller the peeling length 5 is, the better the wet resin adhesion is. However, if the peeling length 5 is less than 10 mm, it is evaluated that the excellent wet resin adhesion intended by the present invention is obtained.
結果を表2に示す。本発明例であるラミネート鋼板No.2〜8では、いずれも優れた湿潤樹脂密着性を示している。これに対し、比較例であるラミネート鋼板No.1は湿潤樹脂密着性に劣っている。 The results are shown in Table 2. In laminated steel sheets Nos. 2 to 8 which are examples of the present invention, all show excellent wet resin adhesion. On the other hand, laminated steel plate No. 1 as a comparative example is inferior in wet resin adhesion.
また、上記実施例とは別に、フッ化チタン酸カリウムに塩化コバルト6水和物または硫酸コバルト7水和物を添加した処理浴で陰極電解処理行った場合にも、優れた湿潤密着性と耐食性を示していることを確認している。 In addition to the above examples, excellent wet adhesion and corrosion resistance are also obtained when cathodic electrolysis is performed in a treatment bath in which cobalt chloride hexahydrate or cobalt sulfate heptahydrate is added to potassium fluorotitanate. Is confirmed.
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
Claims (6)
ここで、湿潤樹脂密着性に優れた皮膜の厚さとは、透過電子顕微鏡(TEM)で観察した皮膜断面プロファイルにおいて、皮膜下面から測定した凸部の最大高さHのことであり、湿潤樹脂密着性に優れた皮膜の凸部の線密度とは、凹部の底の皮膜下面からの最小高さをLとし、(H+L)/2の位置を中心にして±10nmの上下レベルの水平線を引いたとき、下レベルの水平線と断面プロファイルの曲線が交差する隣接の2点間において、上レベルの水平線とプロファイルの曲線が交差する点が1回以上存在する場合に1個の凸部が存在するとして求めた凸部の単位長さあたりの個数のことである。 It is obtained by cathodic electrolysis treatment in an aqueous solution containing at least one metal ion selected from Co, Fe, Ni, V, Cu, Mn and Zn. and has a film excellent wet resin adhesion, including thickness of Ti 20 to 800 nm, and the film excellent in the wet resin adhesion, there is a convex portion 1 / [mu] m or more linear density And a surface-treated steel sheet, characterized in that the mass ratio of Co, Fe, Ni, V, Cu, Mn and Zn to Ti contained in the film excellent in wet resin adhesion is 0.01 to 10 ;
Here, the thickness of the film excellent wet resin adhesion, the coating section profile observed with a transmission electron microscope (TEM), and that the maximum height H of the projection measured from the film lower surface, wet resin adhesion The line density of the convex part of the film with excellent properties is the minimum height from the lower surface of the film at the bottom of the concave part, and the horizontal line at the upper and lower levels of ± 10 nm centered on the position of (H + L) / 2 When it is drawn, there is one convex part when there is at least one point where the upper level horizontal line intersects the profile curve between two adjacent points where the lower level horizontal line intersects the profile profile curve. This is the number of convex portions per unit length obtained as if.
ここで、湿潤樹脂密着性に優れた皮膜の凸部の面密度とは、走査電子顕微鏡(SEM)で観察した皮膜表面のSEM像を3次元解析し、1.0μmのカットオフ波長でフィルター処理を施して求めた凹凸の平均線+0.005μm以上の高さを有する凸部の単位面積あたり個数のことである。 It is obtained by cathodic electrolysis treatment in an aqueous solution containing at least one metal ion selected from Co, Fe, Ni, V, Cu, Mn and Zn. and has a film excellent wet resin adhesion, including thickness of Ti 20 to 800 nm, and the film excellent in the wet resin adhesion, the convex portion 16 / [mu] m 2 or more of the surface density A surface-treated steel sheet, characterized by having a mass ratio of Co, Fe, Ni, V, Cu, Mn, and Zn to Ti contained in the film having excellent wet resin adhesion and 0.01 to 10 ;
Here, the surface density of the convex part of the film with excellent wet resin adhesion means that the SEM image of the film surface observed with a scanning electron microscope (SEM) is three-dimensionally analyzed and filtered with a cutoff wavelength of 1.0 μm. It is the average line of unevenness obtained by applying + the number of convex portions per unit area having a height of 0.005 μm or more.
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