JP4998707B2 - Surface-treated metal plate and manufacturing method thereof, resin-coated metal plate, metal can and can lid - Google Patents
Surface-treated metal plate and manufacturing method thereof, resin-coated metal plate, metal can and can lid Download PDFInfo
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- JP4998707B2 JP4998707B2 JP2007017221A JP2007017221A JP4998707B2 JP 4998707 B2 JP4998707 B2 JP 4998707B2 JP 2007017221 A JP2007017221 A JP 2007017221A JP 2007017221 A JP2007017221 A JP 2007017221A JP 4998707 B2 JP4998707 B2 JP 4998707B2
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- 229910052751 metal Inorganic materials 0.000 title claims description 114
- 239000002184 metal Substances 0.000 title claims description 114
- 229920005989 resin Polymers 0.000 title claims description 64
- 239000011347 resin Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000004381 surface treatment Methods 0.000 claims description 11
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 7
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 claims description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 15
- 238000010828 elution Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 238000012360 testing method Methods 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
- 239000010410 layer Substances 0.000 description 6
- -1 phosphoric acid compound Chemical class 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000007765 extrusion coating Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 238000005211 surface analysis Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000001153 fluoro group Chemical group F* 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
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 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
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000005029 tin-free steel Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004876 x-ray fluorescence Methods 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
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 235000008476 powdered milk Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000002335 surface treatment layer Substances 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
- 238000005496 tempering Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/56—Treatment of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
Description
本発明は、主に缶などの容器に加工して用いられる金属板、特に、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)に優れ、人体にとって極めて害の少ない表面処理金属板およびその製造方法、ならびにこの表面処理金属板に有機樹脂が被覆された樹脂被覆金属板、それを用いた金属缶および缶蓋に関する。 The present invention is a metal plate mainly processed into a container such as a can, particularly a surface treatment that is excellent in adhesion to a resin such as a plastic film (hereinafter referred to as resin adhesion) and extremely harmless to the human body. The present invention relates to a metal plate, a manufacturing method thereof, a resin-coated metal plate in which an organic resin is coated on the surface-treated metal plate, a metal can using the same, and a can lid.
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、クロメート処理を施したSnめっき鋼板やティンフリー鋼板と呼ばれる電解Cr酸処理鋼板などのCr処理缶用金属板が用いられている。 For various metal cans such as beverage cans, food cans, pail cans and 18 liter cans, metal plates for Cr-treated cans such as chromated Sn-plated steel plates and electrolytic Cr-acid treated steel plates called tin-free steel plates are used. ing.
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、製造に6価Crを用いる上記の金属板に対しても代替材が求められている。Crを用いないこれら金属板の代替材として、例えば特許文献1には、MoまたはW、リン酸塩、シラノール基含有化合物を含む皮膜を有する缶用めっき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、リン酸系化合物、フルオロ酸およびシランカップリング剤からなる表面処理用組成物を塗布する金属材料の表面処理方法が提案されている。
In recent years, with the increasing awareness of the environment, the use of hexavalent Cr has been regulated worldwide, and alternative materials are also required for the above metal plates that use hexavalent Cr for production. As an alternative to these metal plates that do not use Cr, for example,
一方、各種金属缶は、従来より、ティンフリー鋼板などの金属板に塗装を施した後に、缶体に加工して製造されていたが、近年、製造に伴う廃棄物の抑制のために、塗装に代わってプラス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金属板(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。このラミネート金属板には、樹脂と金属板が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ラミネート金属板には、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。 On the other hand, various types of metal cans have been manufactured by processing metal cans such as tin-free steel sheets and then processing them into cans. Instead of this, a method of processing a laminated metal plate (resin-coated metal plate) obtained by laminating a resin such as a plastic film into a can body is frequently used. This laminated metal plate requires that the resin and the metal plate are in close contact with each other. In particular, a laminated metal plate used as a beverage can or a food can may undergo a retort sterilization process after filling the contents. For this reason, strong resin adhesion that does not cause the resin to peel even in a high-temperature and humid environment is required.
また、各種缶用金属板は、内容物の腐食性が比較的弱い場合には、Snなどのめっきを施した上で、塗装やラミネートを施さずに用いられる場合もある。例えば、粉ミルクなどの食品を充填する缶にはこの無塗装、無被覆の金属板が用いられることがある。このような金属板では、表面処理皮膜から人体に有害な物質が溶出したり、人体に有害な物質を含む表面処理皮膜の一部が脱落したりしないことが必要である。
しかしながら、特許文献1に記載のMoまたはW、リン酸塩、シラノール基含有化合物を含む皮膜を有する缶用めっき鋼板、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ラミネート鋼板、および特許文献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では、いずれもレトルト雰囲気における樹脂密着性が不十分である。また、特許文献4に記載のリン酸系化合物、フルオロ酸およびシランカップリング剤からなる表面処理用組成物を塗布する表面処理方法による金属材料では、皮膜から人体にとって必須元素の一つであるが、過剰摂取すると有害となるFの溶出の危険性があるため、無塗装、無被覆で飲料缶や食品缶に適用することはできない。
However, Mo or W described in
本発明は、Crを用いず、樹脂密着性に優れ、人体にとって極めて害の少ない、Cr処理缶用金属板の代替材となり得る表面処理金属板およびその製造方法、ならびにこの表面処理金属板に有機樹脂が被覆された樹脂被覆金属板、それを用いた金属缶および缶蓋を提供することを目的とする。 The present invention relates to a surface-treated metal plate that can be used as a substitute for a metal plate for Cr-treated cans, has excellent resin adhesion, is extremely harmless to the human body, and a method for producing the same. An object of the present invention is to provide a resin-coated metal plate coated with a resin, a metal can using the same, and a can lid.
本発明者らは、Crを用いず、樹脂密着性に優れ、人体にとって極めて害の少ない、Cr処理缶用金属板の代替材となり得る表面処理金属板について鋭意研究を重ねた結果、金属板表面にZrおよびOを含む皮膜を形成し、該皮膜のF量を0.1mg/m2未満にすることにより、樹脂密着性に優れ、F溶出の危険性がなく人体にとって極めて害の少ない表面処理金属板が得られることを見出した。 As a result of intensive research on surface-treated metal plates that can be used as substitutes for metal plates for Cr treatment cans, which do not use Cr, have excellent resin adhesion, and are extremely harmless to the human body, By forming a film containing Zr and O on the surface and making the F amount of this film less than 0.1 mg / m 2 , it is a surface-treated metal that has excellent resin adhesion, has no danger of F elution, and is extremely harmless to the human body It was found that a plate was obtained.
本発明は、このような知見に基づきなされたもので、電気Snめっき鋼板の少なくとも片面に、ZrおよびOを含み、残部が不可避的不純物からなる皮膜を有し、該皮膜のF量が片面あたり0.1mg/m 2 未満であることを特徴とする表面処理金属板を提供する。 The present invention has been made based on such findings, the at least one surface of the electro-Sn-plated steel sheet includes Zr and O, the balance have a coating consisting of inevitable impurities, per one side F of said coating Provided is a surface-treated metal sheet characterized by being less than 0.1 mg / m 2 .
本発明の表面処理金属板では、ZrおよびOを含み、残部が不可避的不純物からなる皮膜のZr量は片面あたり3〜200mg/m2であることが好ましい。 In the surface-treated metal plate of the present invention, it is preferable that the Zr amount of the coating containing Zr and O and the balance of inevitable impurities is 3 to 200 mg / m 2 per side.
本発明は、また、本発明の表面処理金属板のZrおよびOを含み、残部が不可避的不純物からなる皮膜上に、有機樹脂が被覆されている樹脂被覆金属板、それを用いた金属缶および缶蓋を提供する。 The present invention also includes a resin-coated metal plate containing Zr and O of the surface-treated metal plate of the present invention , the balance being made of inevitable impurities , and an organic resin coated thereon, a metal can using the same, and Provide a can lid.
本発明の表面処理金属板は、例えば、電気Snめっき鋼板の少なくとも片面に、酢酸ジルコニル、硝酸ジルコニル、塩化酸化ジルコニウムから選ばれた少なくとも1種からなる水溶液を用いて、陰極電解処理または浸漬処理を施すことによりZrおよびOを含み、残部が不可避的不純物からなる皮膜を形成し、該皮膜のF量を片面あたり0.1mg/m 2 未満にすることで製造できる。 The surface-treated metal plate of the present invention is, for example, subjected to cathodic electrolysis treatment or immersion treatment using an aqueous solution of at least one selected from zirconyl acetate, zirconyl nitrate, and zirconium chloride oxide on at least one surface of an electric Sn-plated steel plate. It can be produced by forming a film containing Zr and O, the balance being inevitable impurities, and making the F content of the film less than 0.1 mg / m 2 per side .
本発明により、Crを用いず、樹脂密着性に優れ、人体にとって極めて害の少ない表面処理金属板を製造できるようになった。本発明の表面処理金属板は、従来のCr処理缶用金属板の代替材として問題なく、有機樹脂を被覆して樹脂被覆金属板とし、金属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。また、本発明の表面処理金属板は、過剰摂取すると人体に有害となるFの溶出が起こらないので、無塗装、無被覆で飲料缶や食品缶に適用できる。 The present invention makes it possible to produce a surface-treated metal plate that does not use Cr, has excellent resin adhesion, and is extremely harmless to the human body. The surface-treated metal plate of the present invention has no problem as an alternative to the conventional metal plate for Cr-treated cans, and is coated with an organic resin to form a resin-coated metal plate. Can be processed without any occurrence. In addition, since the surface-treated metal plate of the present invention does not cause elution of F, which is harmful to the human body when excessively consumed, it can be applied to beverage cans and food cans without coating or coating.
1)表面処理金属板
本発明の表面処理金属板では、金属板表面にZrおよびOを含む皮膜が形成されているが、Zr主体の皮膜とすることにより金属板の樹脂密着性が向上し、また、皮膜のF量を片面あたり0.1mg/m2未満とすることにより、無塗装、無被覆で用いてもFの溶出が起こらず、人体にとって有害となることはない。
1) Surface-treated metal plate In the surface-treated metal plate of the present invention, a film containing Zr and O is formed on the surface of the metal plate, but by using a Zr-based film, the resin adhesion of the metal plate is improved, In addition, by setting the F amount of the film to less than 0.1 mg / m 2 per side, F is not eluted even if it is used uncoated or uncoated, and it is not harmful to the human body.
金属板としては、一般的な缶用の鋼板、Al板、Al合金板などを用いることができる。特に、耐食性確保のため、電気Snめっき鋼板を用いることが好ましい。 As the metal plate, a general steel plate for cans, an Al plate, an Al alloy plate, or the like can be used. In particular, it is preferable to use an electric Sn-plated steel sheet in order to ensure corrosion resistance.
金属板表面に形成されたZrおよびOを含む皮膜のZr量は、片面あたり、3mg/m2未満だと樹脂密着性の改善効果が不十分であり、200mg/m2を超えると更なる樹脂密着性の向上が望めず、コスト高となる場合があるので、3〜200mg/m2であることが好ましい。 If the Zr content of the coating containing Zr and O formed on the surface of the metal plate is less than 3 mg / m 2 per side, the effect of improving the resin adhesion is insufficient, and if it exceeds 200 mg / m 2 , the resin becomes more resinous. Since improvement in adhesion cannot be expected and the cost may increase, it is preferably 3 to 200 mg / m 2 .
ZrおよびOを含む皮膜の形成方法としては、Zrが含有され、F量が0.03mo1/l未満である水溶液を用いて、金属板を陰極電解処理または浸漬処理を施す方法等が好適である。Zrが含有され、F量が0.03mo1/l未満である水溶液を用いることにより、皮膜のF量を0.1mg/m2未満とすることができる。なお、皮膜のZr量は、陰極電解処理する方法では電流密度や電解時間を変えることにより、浸漬処理では浸漬時間を変えることにより、調整可能である。また、皮膜のZr量は、蛍光X線による表面分析により測定できる。皮膜のO量は、XPSによる表面分析でその存在を確認できる。皮膜のF量は、XPSにより皮膜表面におけるZrとFの元素比を測定し、上記の蛍光X線分析で測定したZr量を基に算出できる。 As a method for forming a film containing Zr and O, a method of subjecting a metal plate to cathodic electrolysis treatment or immersion treatment using an aqueous solution containing Zr and having an F content of less than 0.03 mo1 / l is suitable. By using an aqueous solution containing Zr and having an F content of less than 0.03 mo1 / l, the F content of the coating can be made less than 0.1 mg / m 2 . The amount of Zr in the film can be adjusted by changing the current density and electrolysis time in the method of cathodic electrolysis treatment and by changing the immersion time in the immersion treatment. The amount of Zr in the film can be measured by surface analysis using fluorescent X-rays. The amount of O in the film can be confirmed by surface analysis by XPS. The F amount of the film can be calculated based on the Zr amount measured by the X-ray fluorescence analysis described above by measuring the element ratio of Zr and F on the film surface by XPS.
上記のZrが含有された水溶液には、酢酸ジルコニル、硝酸ジルコニル、塩化酸化ジルコニウム等のジルコニウム化合物を含有した水溶液を用いることができる。特に、酢酸ジルコニルを含む水溶液中で金属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 the aqueous solution containing Zr, an aqueous solution containing a zirconium compound such as zirconyl acetate, zirconyl nitrate, zirconium chloride or the like can be used. In particular, the method of cathodic electrolysis of a metal plate in an aqueous solution containing zirconyl acetate is preferable because it can form a uniform film efficiently.
2)樹脂被覆金属板(ラミネート金属板)
本発明の表面処理金属板上に、有機樹脂を被覆して樹脂被覆金属板とすることができる。上述したように、本発明の表面処理金属板は樹脂密着性に優れているため、この樹脂被覆金属板は優れた耐食性と加工性を有する。
2) Resin-coated metal plate (laminated metal plate)
The surface-treated metal plate of the present invention can be coated with an organic resin to form a resin-coated metal plate. As described above, since the surface-treated metal plate of the present invention is excellent in resin adhesion, the resin-coated metal plate has excellent corrosion resistance and workability.
本発明の表面処理金属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の範囲で表面処理金属板側、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。 There is no limitation in particular as organic resin coat | covered on the surface treatment metal plate of this invention, Various thermoplastic resins and thermosetting resins can be mentioned. 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 It may be a non-stretched or biaxially stretched thermoplastic resin film such as a polyamide film such as nylon 6,6, nylon 11, or nylon 12, a polyvinyl chloride film, or a polyvinylidene chloride film. 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 metal 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、表面処理金属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、表面処理金属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金属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金属板を通し、その両側に溶融樹脂ウエッブを供給することにより、前記表面処理金属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 formation of the organic resin coating layer on the surface-treated metal plate can be performed 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. it can. 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 metal plate and thermally bonding it. That is, after melt-kneading the organic resin with an extruder, it is extruded from the T-die into a thin film, and the extruded molten resin film is passed through a pair of laminating rolls with a surface-treated metal plate to be pressed and integrated under cooling, Then quench rapidly. 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 metal plate by passing a surface-treated metal plate vertically between a pair of laminate rolls and supplying a molten resin web to both sides thereof.
3)金属缶および缶蓋
本発明の金属缶は、前述した樹脂被覆金属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。この金属缶は、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、表面処理金属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) Metal can and can lid As long as the metal can of the present invention is formed from the above-mentioned resin-coated metal plate, any can-making method may be used. The metal 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 organic resin coating surface of the surface-treated metal plate is on the inside of the can. -It is manufactured by attaching to a conventionally known means such as ironing or drawing / ironing.
また、本発明の缶蓋は、上述した樹脂被覆金属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。 The can lid of the present invention may be formed by any conventionally known lid-making method as long as it is formed from the above-described resin-coated metal plate. 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.
金属板として、
A:板厚0.20mm、調質度T-4の低炭素冷延鋼板
B:板厚0.22mm、Sn付着量2.8g/m2(片面)の電気Snめっき鋼板
C:板厚0.28mmのAl板(JIS5021H18)
を使用し、アルカリ脱脂、酸洗を施した後(ただし、金属板Bには酸洗を省略)、表1に示す組成の処理液中で、同じく表1に示す条件で陰極電解処理または浸漬処理を行い、水洗してZrおよびOを含有した皮膜を金属板の両面に形成し、表面処理金属板No.1〜6を作製した。ここで、陰極電解処理の際には、陽極にPt被覆したTiを用いた。
As a metal plate,
A: Low carbon cold-rolled steel sheet with a thickness of 0.20mm and tempering grade T-4
B: Electric Sn-plated steel sheet with a thickness of 0.22mm and Sn coverage of 2.8g / m 2 (single side)
C: 0.28mm thick Al plate (JIS5021H18)
After performing alkaline degreasing and pickling (however, pickling is omitted for the metal plate B), in the treatment liquid having the composition shown in Table 1, and cathodic electrolytic treatment or immersion under the same conditions as shown in Table 1. The surface treatment metal plate No. 1-6 was produced by processing, washing with water, and forming the film containing Zr and O on both surfaces of the metal plate. Here, in the cathode electrolysis treatment, Ti coated with Pt on the anode was used.
比較のため、表2に示す条件で金属板に電解処理を行い、一部の金属板(No.7)を除いて、その後、表2に示す組成の浸漬処理液に1sec間浸漬して、表面処理金属板No.7〜9を作製した。ここで、表面処理金属板No．7では、陰極電解処理によりW、リン酸塩およびシラノール基を含む有機化合物を含有する皮膜が、表面処理金属板No．8では、陽極電解処理後、リン酸マグネシウム水溶液に浸漬処理を行ってMg含有皮膜が形成されている。表面処理金属板No．9では、陰極電解処理によりSn皮膜が形成された後、浸漬処理によりTi含有フェノール樹脂皮膜が形成されている。表面処理金属板No．10では、塗布処理によりシランカップリング剤処理層(付着量:0.5g/m2)が形成されている。 For comparison, the metal plate was subjected to electrolytic treatment under the conditions shown in Table 2, except for some metal plates (No. 7), and then immersed in an immersion treatment liquid having the composition shown in Table 2 for 1 second. Surface-treated metal plates No. 7 to 9 were produced. Here, the surface-treated metal plate No. In No. 7, a film containing an organic compound containing W, phosphate, and silanol groups by cathodic electrolysis was formed on the surface-treated metal plate No. 7. In No. 8, after the anodic electrolytic treatment, a magnesium-containing film is formed by immersing in an aqueous magnesium phosphate solution. Surface-treated metal plate No. In No. 9, after the Sn film is formed by cathodic electrolysis, a Ti-containing phenol resin film is formed by dipping. Surface-treated metal plate No. In No. 10, a silane coupling agent treatment layer (adhesion amount: 0.5 g / m 2 ) is formed by coating treatment.
表面処理金属板No.1〜6の皮膜のZr量、No.7の皮膜のW、P、Si量、No.8の皮膜のMg量、No.9の皮膜のSn、Ti量、No.10の皮膜のZr、Si量の測定は、それぞれ予め付着量を湿式分析して求めた検量板との比較による蛍光Ｘ線分析により行った。No.1〜6の皮膜のOは、XPSによる表面分析でその存在を確認した。No.1〜6、10の皮膜のF量は、XPSにより皮膜表面におけるZrとFの元素比を測定し、上記の蛍光X線分析で測定したZr量を基に算出した。皮膜のZr量、F量、W量、P量、Si量、Mg量、Sn量、Ti量を表1、2に示す。 Surface treated metal plate No. 1-6 Zr amount, No. 7 W, P, Si amount, No. 8 Mg amount, No. 9 Sn, Ti amount, No. The Zr and Si amounts of the 10 coatings were measured by fluorescent X-ray analysis by comparison with a calibration plate obtained by wet analysis of the adhesion amount in advance. The presence of O in the films No. 1 to 6 was confirmed by XPS surface analysis. The F amounts of the films Nos. 1 to 6 and 10 were calculated based on the Zr amounts measured by the above X-ray fluorescence analysis by measuring the element ratio of Zr and F on the film surface by XPS. Tables 1 and 2 show the Zr content, F content, W content, P content, Si content, Mg content, Sn content, and Ti content of the coating.
これらの表面処理金属板No.1〜10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、ラミネート金属板(樹脂被覆金属板)No.1〜10を作製した。ラミネートは、210℃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金属板に融着させ、ゴムロール通過後1sec以内に水冷して行った。このとき、金属板の送り速度は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、ゴムロールと金属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金属板No.1〜10について、次の樹脂密着性の評価を行った。
樹脂密着性評価：温度130℃、相対湿度100%のレトルト雰囲気における180°ピール試験により樹脂密着性の評価を行った。180°ピール試験とは、図1の(a)に示すようなフィルム2を残して金属板1の一部3を切リ取った試験片(サイズ：30mm×100mm)を用い、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間放置して行うフィルム剥離試験のことである。そして、図1の(c)に示す剥離長5を測定し、次のように樹脂密着性を評価し、◎または○であれば樹脂密着性が良好であるとした。
◎：剥離長が15mm未満
○：剥離長が15mm以上 20mm未満
△：剥離長が20mm以上50mm未満
×：剥離長が50mm以上
また、有機樹脂被覆層がラミネートされる前の表面処理金属板No.1〜10について、以下の方法でF溶出量を測定した。
F溶出量：50×50mmの試験片を1mass%クエン酸水溶液100ml中に4枚浸漬し、密封して55℃で72hr放置した後、溶液中のF量をICPにより測定した。溶出したF量が0.01mg未満であれば問題なし(○)、0.01mg以上であれば問題となる可能性あり(×)とした。
Laminated metal plates (resin coating) were laminated on both surfaces of these surface-treated metal plates No. 1 to 10 with an isophthalic acid copolymerized polyethylene terephthalate film (organic resin coating layer) having a thickness of 25 μm and a copolymerization ratio of 12 mol%. Metal plates No. 1 to 10 were produced. Lamination was performed by sandwiching a metal plate heated to 210 ° C. and a film between a pair of rubber rolls, fusing the film to the metal plate, and cooling with water within 1 sec after passing through the rubber roll. At this time, the feed speed of the metal 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 metal plate are in contact. And about the produced laminated metal plate No. 1-10, the following resin adhesiveness evaluation was performed.
Resin adhesion evaluation: Resin adhesion was 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 × 100 mm) obtained by cutting off a part 3 of the
◎: Peel length is less than 15mm ○: Peel length is 15mm or more and less than 20mm △: Peel length is 20mm or more and less than 50mm ×: Peel length is 50mm or more Also, the surface-treated metal plate No. before the organic resin coating layer is laminated About 1-10, the F elution amount was measured with the following method.
F elution amount: Four test pieces of 50 × 50 mm were immersed in 100 ml of 1 mass% citric acid aqueous solution, sealed and allowed to stand at 55 ° C. for 72 hours, and then the F amount in the solution was measured by ICP. If the amount of F eluted was less than 0.01 mg, there was no problem (O), and if it was 0.01 mg or more, there was a possibility of a problem (x).
樹脂密着性とF溶出量の評価結果を表3に示す。本発明例であるラミネートされた金属板No.2、5、6では、いずれも良好な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された金属板No.7〜9は、樹脂密着性に劣っている。また、ラミネートされる前のこれらの金属板No.1〜9は、皮膜中にFを含まないため、ラミネートせずに使用しても問題はない。一方、ラミネートされた金属板No.10は、比較的良好な樹脂密着性を示しているが、ラミネートされる前の金属板では、Fの溶出量が多く、ラミネートせずに使用すると問題となる可能性がある。 Table 3 shows the evaluation results of resin adhesion and F elution amount. In the laminated metal plates No. 2 , 5 , and 6 , which are examples of the present invention, all show good resin adhesion. On the other hand, laminated metal plates No. 7 to 9, which are comparative examples, are inferior in resin adhesion. Moreover, since these metal plates No. 1 to 9 before being laminated do not contain F in the film, there is no problem even if they are used without being laminated. On the other hand, the laminated metal plate No. 10 shows relatively good resin adhesion, but the metal plate before lamination has a large amount of F elution, which causes a problem when used without lamination. there is a possibility.
実施例1で作製したラミネート金属板No.1〜4、7、9を用いて、表4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、同じラミネート金属板を用いて、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。作製した金属缶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、金属缶に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。 Using the laminated metal plates No. 1 to 4, 7, and 9 produced in Example 1, the can is processed under the conditions shown in Table 4, and the opening end of the can body is necked in and flanged to make a metal seamless can No. 1-6 were produced. Also, using the same laminated metal 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. The produced metal cans Nos. 1 to 6 and the lids were visually inspected for abnormalities such as peeling of the film after the can making and perforation. After filling a metal can with a coffee drink at 50 ° C, double-wrap the lid, perform a retort treatment at 125 ° C for 25 min, leave it at 37 ° C for 6 months, and then open the can. Corrosion and film abnormalities were examined visually.
結果を表5に示す。本発明であるラミネート金属板を用いた金属缶No.2には、製缶後および内容物充填後に金属缶および蓋を調べたが、いずれにおいてもフィルム異常は確認できなかった。 The results are shown in Table 5. For metal can No. 2 using the laminated metal plate according to the present invention, the metal can and the lid were examined after making the can and after filling the contents, but no film abnormality was confirmed in any case.
一方、本発明でないラミネート金属板を用いた金属缶No.5、6では、製缶後にフィルム異常や、内容物充填後にフィルム異常(剥離)と腐食が確認された。 On the other hand, in metal cans Nos. 5 and 6 using a laminated metal plate that is not the present invention, film abnormality after making the can and film abnormality (peeling) and corrosion after filling the contents were confirmed.
1 金属板
2 フィルム
3 金属板の切リ取った部位
4 重り
5 剥離長
1 Metal plate
2 film
3 Parts cut out of a metal plate
4 weights
5 Peel length
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| JP5786296B2 (en) * | 2010-03-25 | 2015-09-30 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet, method for producing the same, and resin-coated steel sheet using the same |
| WO2011126137A1 (en) * | 2010-04-06 | 2011-10-13 | 新日本製鐵株式会社 | Process for production of steel sheet for container material which has reduced load on environments, steel sheet for container material which has reduced load on environments, and laminate steel sheet for container material and coated precoat steel sheet for container material which are produced using the steel sheet |
| CN103097583B (en) * | 2010-09-15 | 2015-11-25 | 杰富意钢铁株式会社 | Steel plate for container and manufacture method thereof |
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| WO2014024282A1 (en) * | 2012-08-08 | 2014-02-13 | 日本パーカライジング株式会社 | Metal surface treatment liquid, surface treatment method for metal bases, and metal base obtained by surface treatment method for metal bases |
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| JP5773093B2 (en) | 2013-07-24 | 2015-09-02 | Ｊｆｅスチール株式会社 | Steel plate for containers |
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| WO2017078105A1 (en) * | 2015-11-06 | 2017-05-11 | 新日鐵住金株式会社 | Aqueous surface treatment agent for zinc plated steel material or zinc-based alloy plated steel material, coating method, and coated steel material |
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