JP2014111823A - Steel sheet for vessel, process liquid used for manufacturing the steel sheet, and manufacturing method of the steel sheet for vessel - Google Patents
Steel sheet for vessel, process liquid used for manufacturing the steel sheet, and manufacturing method of the steel sheet for vessel Download PDFInfo
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- JP2014111823A JP2014111823A JP2013152771A JP2013152771A JP2014111823A JP 2014111823 A JP2014111823 A JP 2014111823A JP 2013152771 A JP2013152771 A JP 2013152771A JP 2013152771 A JP2013152771 A JP 2013152771A JP 2014111823 A JP2014111823 A JP 2014111823A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 148
- 239000010959 steel Substances 0.000 title claims abstract description 148
- 239000007788 liquid Substances 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000007747 plating Methods 0.000 claims abstract description 86
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 238000001228 spectrum Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 238000005868 electrolysis reaction Methods 0.000 claims description 29
- 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 10
- 238000012545 processing Methods 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 150000003609 titanium compounds Chemical class 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 36
- 229920005989 resin Polymers 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 86
- 229910052718 tin Inorganic materials 0.000 description 70
- 238000002845 discoloration Methods 0.000 description 23
- 238000012360 testing method Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 229910000576 Laminated steel Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 titanium alkoxide Chemical class 0.000 description 5
- 229910017091 Fe-Sn Inorganic materials 0.000 description 4
- 229910017142 Fe—Sn Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000005211 surface analysis Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 229910003271 Ni-Fe Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 3
- 235000015193 tomato juice Nutrition 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229910020938 Sn-Ni Inorganic materials 0.000 description 2
- 229910008937 Sn—Ni Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 238000010030 laminating Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- YOBCTIIWHLYFII-UHFFFAOYSA-L difluorotitanium Chemical compound F[Ti]F YOBCTIIWHLYFII-UHFFFAOYSA-L 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- ZHHHHWLNNWAEML-UHFFFAOYSA-L dipotassium;oxalate;dihydrate Chemical compound O.O.[K+].[K+].[O-]C(=O)C([O-])=O ZHHHHWLNNWAEML-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明は、容器用鋼板、その製造に用いられる処理液、および、容器用鋼板の製造方法に関する。 The present invention relates to a steel plate for containers, a treatment liquid used for manufacturing the same, and a method for manufacturing a steel plate for containers.
容器用鋼板（缶用表面処理鋼板）としては、従来から「ぶりき」と称される錫めっき鋼板が広く用いられている。このような錫めっき鋼板では、通常、重クロム酸などの６価のクロム化合物を含有する水溶液中に鋼板を浸漬する、または、この溶液中で電解処理を行うなどのクロメート処理によって、錫めっき表面にクロメート皮膜が形成される。
しかしながら、昨今の環境問題を踏まえて、Ｃｒの使用を規制する動きが各分野で進行しており、容器用鋼板においてもクロメート処理に替わる処理技術がいくつか提案されている。
例えば、特許文献１には、「Ｃｒを用いず、樹脂密着性に優れ」るものとして（［００１３］）、「金属板の少なくとも片面に、ＺｒおよびＯを含む皮膜を有し、該皮膜のＦ量が片面あたり０．１ｍｇ／ｍ2未満であることを特徴とする表面処理金属板」が開示されており（［請求項１］）、ここでいう「金属板」は「電気Ｓｎめっき鋼板」である（［請求項３］）。
As a steel plate for containers (surface-treated steel plate for cans), a tin-plated steel plate conventionally referred to as “blink” has been widely used. In such a tin-plated steel plate, the surface of the tin-plated surface is usually obtained by immersing the steel plate in an aqueous solution containing a hexavalent chromium compound such as dichromic acid, or by performing a chromate treatment such as performing an electrolytic treatment in this solution. A chromate film is formed on the surface.
However, in light of recent environmental problems, movements for restricting the use of Cr have progressed in various fields, and several treatment techniques for replacing chromate treatment have been proposed for steel plates for containers.
For example,
近年、消費者の美観に関する要求の高まりによって、容器用鋼板に求められる種々の特性について、より一層の向上が求められている。
本発明者らは、特許文献１に開示された容器用鋼板（表面処理金属板）について、さらに検討を行なった。その結果、ＰＥＴフィルム等の樹脂をラミネートした後にレトルト処理を行なった際に、樹脂であるフィルムに対する密着性（以下「樹脂密着性」ともいう）が不十分となる場合があることが分かった。
また、本発明者らは、ラミネート後の容器用鋼板を所定条件下でトマトジュースに浸漬すると、樹脂であるフィルムが変色する場合があり、変色に対する耐性（以下「耐変色性」ともいう）に劣ることが分かった。このとき、本発明者らは、この変色が、めっき層に含まれる錫（Ｓｎ）の酸化によるものであることを見出した。
In recent years, with the increasing demand for consumer aesthetics, further improvements have been required for various properties required for steel plates for containers.
The inventors further studied the steel plate for containers (surface-treated metal plate) disclosed in
In addition, when the present inventors immerse the laminated steel plate in tomato juice under a predetermined condition, the resin film may be discolored, which is resistant to discoloration (hereinafter also referred to as “discoloration resistance”). I found it inferior. At this time, the present inventors have found that this discoloration is due to oxidation of tin (Sn) contained in the plating layer.
本発明は、以上の点を鑑みてなされたものであり、樹脂密着性および耐変色性に優れる容器用鋼板を提供することを目的とする。 This invention is made | formed in view of the above point, and it aims at providing the steel plate for containers excellent in resin adhesiveness and discoloration resistance.
本発明者らは、上記目的を達成するために鋭意検討を行なった結果、容器用鋼板の皮膜が、特定比のＺｒおよびＴｉを有し、さらにカルボニル基を含むことで、樹脂密着性および耐変色性がいずれも良好となることを見出し、本発明を完成させた。
すなわち、本発明は、以下の（１）〜（１１）を提供する。
As a result of intensive studies to achieve the above object, the present inventors have found that the coating of the steel plate for containers has a specific ratio of Zr and Ti, and further contains a carbonyl group, so that resin adhesion and resistance The present inventors have found that the discoloration is good and completed the present invention.
That is, the present invention provides the following (1) to (11).
（１）鋼板および上記鋼板の表面の少なくとも一部を覆う錫めっき層を有する錫めっき層付き鋼板と、上記錫めっき層付き鋼板の上記錫めっき層側の表面上に配置された皮膜とを有する容器用鋼板であって、上記皮膜が、ＺｒおよびＴｉを有し、上記皮膜は、上記錫めっき層付き鋼板の片面あたりのＺｒ換算の付着量が１．０〜４０．０ｍｇ／ｍ2であって、上記錫めっき層付き鋼板の片面あたりのＴｉ換算の付着量が０．０１ｍｇ／ｍ2以上８．０ｍｇ／ｍ2未満であり、上記皮膜のＴｉとＺｒとの質量比（Ｔｉ／Ｚｒ）が０．０１以上０．２０未満であり、上記皮膜の赤外線吸収（ＩＲ）スペクトルにおいて、波数１５５０〜１８００ｃｍ-1の範囲にカルボニル基（Ｃ＝Ｏ）に由来する吸収ピークを示すことを特徴とする容器用鋼板。
（２）上記皮膜のＺｒ１モルに対して、上記カルボニル基の量が０．６モル以上１．２モル未満である、上記（１）に記載の容器用鋼板。
（３）上記皮膜の鋼板側とは反対の最表面におけるＴｉとＺｒとの原子比（Ｔｉ／Ｚｒ）が、０．０５以上０．４０未満である、上記（１）または（２）に記載の容器用鋼板。
（４）上記皮膜中のリン量が、１０．０ｍｇ／ｍ2以下である、上記（１）〜（３）のいずれかに記載の容器用鋼板。
（５）上記皮膜中のフッ素量が、０．２ｍｇ／ｍ2未満である、上記（１）〜（４）のいずれかに記載の容器用鋼板。
（６）上記錫めっき層付き鋼板が、表面にニッケル含有層を有する鋼板を用いて形成された、上記（１）〜（５）のいずれかに記載の容器用鋼板。
（７）上記（１）〜（６）のいずれかに記載の容器用鋼板の製造に用いられる処理液であって、オキシ酢酸ジルコニウムと、チタン化合物とを含有することを特徴とする、処理液。
（８）さらに、硝酸イオンである陰イオンと、カリウムイオン、アンモニウムイオンおよびナトリウムイオンからなる群から選ばれる少なくとも１種の陽イオンと、を含有する、上記（７）に記載の処理液。
（９）上記オキシ酢酸ジルコニウムの含有量が、０．３〜１５．０ｇ／Ｌであり、上記チタン化合物の含有量が、２×１０-5〜１×１０-3ｍｏｌ／Ｌである、上記（７）または（８）に記載の処理液。
（１０）上記（１）〜（６）のいずれかに記載の容器用鋼板を得る、容器用鋼板の製造方法であって、上記（７）〜（９）のいずれかに記載の処理液中に上記錫めっき層付き鋼板を浸漬する、または、浸漬した上記錫めっき層付き鋼板に陰極電解処理を施すことにより、上記皮膜を形成することを特徴とする容器用鋼板の製造方法。
（１１）上記陰極電解処理を施す際の電解電流密度が、０．０５〜７．０Ａ／ｄｍ2であり、上記陰極電解処理の通電時間が、０．１〜５秒である、上記（１０）に記載の容器用鋼板の製造方法。
(1) A steel plate with a tin plating layer having a tin plating layer covering at least a part of the surface of the steel plate and the steel plate, and a film disposed on the surface of the steel plate with the tin plating layer on the tin plating layer side. It is a steel plate for containers, and the coating has Zr and Ti, and the coating has a Zr equivalent adhesion amount of 1.0 to 40.0 mg / m 2 per one side of the steel plate with the tin plating layer. In addition, the amount of Ti converted per one side of the steel sheet with the tin plating layer is 0.01 mg / m 2 or more and less than 8.0 mg / m 2 , and the mass ratio of Ti and Zr of the film (Ti / Zr) In the infrared absorption (IR) spectrum of the film, the absorption peak derived from a carbonyl group (C═O) is shown in the range of wave numbers 1550 to 1800 cm −1. Steel plate for containers.
(2) The steel plate for containers according to (1) above, wherein the amount of the carbonyl group is 0.6 mol or more and less than 1.2 mol with respect to 1 mol of Zr of the coating.
(3) The atomic ratio (Ti / Zr) between Ti and Zr on the outermost surface opposite to the steel plate side of the coating is 0.05 or more and less than 0.40, as described in (1) or (2) above. Steel plate for containers.
(4) The steel plate for containers according to any one of (1) to (3) above, wherein the amount of phosphorus in the film is 10.0 mg / m 2 or less.
(5) Fluorine content in the film is less than 0.2 mg / m 2, the container for steel sheet according to any one of the above (1) to (4).
(6) The steel plate for containers according to any one of (1) to (5), wherein the steel plate with a tin plating layer is formed using a steel plate having a nickel-containing layer on the surface.
(7) A treatment liquid used in the production of the steel plate for containers according to any one of (1) to (6) above, which contains zirconium oxyacetate and a titanium compound. .
(8) The treatment liquid according to (7), further comprising an anion that is a nitrate ion and at least one cation selected from the group consisting of potassium ion, ammonium ion, and sodium ion.
(9) The content of the zirconium oxyacetate is 0.3 to 15.0 g / L, and the content of the titanium compound is 2 × 10 −5 to 1 × 10 −3 mol / L. (7) or the processing liquid according to (8).
(10) A method for producing a steel plate for a container according to any one of (1) to (6) above, wherein the processing solution according to any one of (7) to (9) above is obtained. A method for producing a steel plate for containers, comprising: dipping the steel plate with a tin plating layer into the plate or subjecting the immersed steel plate with a tin plating layer to cathodic electrolysis.
(11) The above-mentioned (10), wherein an electrolysis current density at the time of performing the cathode electrolysis treatment is 0.05 to 7.0 A / dm 2 , and an energization time of the cathode electrolysis treatment is 0.1 to 5 seconds. The manufacturing method of the steel plate for containers as described in a.
本発明によれば、樹脂密着性および耐変色性に優れる容器用鋼板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the steel plate for containers excellent in resin adhesiveness and discoloration resistance can be provided.
〔容器用鋼板〕
本発明の容器用鋼板は、錫めっき層付き鋼板と、錫めっき層付き鋼板の錫めっき層側の表面上に配置された皮膜とを有する。そして、この皮膜が、ＺｒおよびＴｉを特定比で含有し、さらに、カルボニル基（Ｃ＝Ｏ）を含むことにより、樹脂密着性および耐変色性に優れる。
上記効果が得られるメカニズムは明らかではないが、皮膜中に析出するＴｉ化合物が大きな比表面積かつ針状の形状を有しており、この化合物によるアンカー効果によって樹脂（フィルム）と皮膜との密着性が向上する、樹脂と皮膜との界面において高温下での水分の拡散が抑制されることで錫めっき層におけるＳｎの酸化が抑制される、皮膜中でＺｒとの複合化合物を形成することで上記効果が相乗的に向上する等の理由が考えられる。
また、皮膜中に含まれるカルボニル基によって、皮膜表面の親水性が低下することで、水分の拡散が抑制されると考えられる。さらに、カルボニル基の存在によって樹脂フィルム、特にポリエステル系フィルムとの相溶性が向上し、その結果密着性が向上すると考えられる。
なお、上記メカニズムは推測であり、上記メカニズム以外であっても本発明の範囲内であるとする。
[Steel plate for containers]
The steel plate for containers of the present invention has a steel plate with a tin plating layer and a film disposed on the surface on the tin plating layer side of the steel plate with a tin plating layer. And this film | membrane is excellent in resin adhesiveness and discoloration resistance by containing Zr and Ti by specific ratio, and also including a carbonyl group (C = O).
Although the mechanism by which the above effect is obtained is not clear, the Ti compound deposited in the film has a large specific surface area and a needle-like shape, and the adhesion between the resin (film) and the film due to the anchor effect of this compound The formation of a composite compound with Zr in the film suppresses the oxidation of Sn in the tin plating layer by suppressing the diffusion of moisture at a high temperature at the interface between the resin and the film. The reason is that the effect is synergistically improved.
Moreover, it is thought that the diffusion of moisture is suppressed by the decrease in hydrophilicity of the coating surface due to the carbonyl group contained in the coating. Furthermore, the presence of a carbonyl group is considered to improve compatibility with a resin film, particularly a polyester film, and as a result, improve adhesion.
Note that the above mechanism is speculative, and it is assumed that the mechanism other than the above mechanism is within the scope of the present invention.
以下に、錫めっき層付き鋼板、および、皮膜の具体的な態様について詳述する。まず、錫めっき層付き鋼板の態様について詳述する。 Below, the steel plate with a tin plating layer and the specific aspect of a membrane | film | coat are explained in full detail. First, the aspect of the steel plate with a tin plating layer is explained in full detail.
＜錫めっき層付き鋼板＞
錫めっき層付き鋼板は、鋼板および鋼板の表面の少なくとも一部を覆う錫めっき層を有する。以下に、鋼板および錫めっき層の態様について詳述する。
<Steel-coated steel sheet>
The steel sheet with a tin plating layer has a tin plating layer that covers at least a part of the surface of the steel sheet and the steel sheet. Below, the aspect of a steel plate and a tin plating layer is explained in full detail.
（鋼板）
錫めっき層付き鋼板中の鋼板の種類は特に制限されるものではなく、通常、容器材料として使用される鋼板（例えば、低炭素鋼板、極低炭素鋼板）を用いることができる。この鋼板の製造方法、材質なども特に規制されるものではなく、通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。
(steel sheet)
The type of the steel plate in the steel plate with the tin plating layer is not particularly limited, and a steel plate (for example, a low carbon steel plate or an extremely low carbon steel plate) that is usually used as a container material can be used. The manufacturing method and material of the steel plate are not particularly restricted, and the steel plate is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling from a normal steel slab manufacturing process.
鋼板は、必要に応じて、その表面にニッケル（Ｎｉ）含有層を形成したものを用い、該Ｎｉ含有層上に錫めっき層を形成してもよい。Ｎｉ含有層を有する鋼板を用いて錫めっきを施すことにより、島状Ｓｎを含む錫めっき層を形成することでき、溶接性が向上する。
Ｎｉ含有層としてはニッケルが含まれていればよく、例えば、Ｎｉめっき層、Ｎｉ−Ｆｅ合金層などが挙げられる。
鋼板にＮｉ含有層を付与する方法は特に制限されず、例えば、公知の電気めっきなどの方法が挙げられる。また、Ｎｉ含有層としてＮｉ−Ｆｅ合金層を付与する場合、電気めっきなどにより鋼板表面上にＮｉ付与後、焼鈍することにより、Ｎｉ拡散層を配位させ、Ｎｉ−Ｆｅ合金層を形成することができる。
Ｎｉ含有層中のＮｉ量は特に制限されず、片面当たりの金属Ｎｉ換算量として５０〜２０００ｍｇ／ｍ2が好ましい。上記範囲内であれば、耐硫化黒変性により優れ、コスト面でも有利となる。
If necessary, a steel sheet having a nickel (Ni) -containing layer formed on the surface thereof may be used, and a tin plating layer may be formed on the Ni-containing layer. By performing tin plating using a steel sheet having a Ni-containing layer, a tin plating layer containing island-shaped Sn can be formed, and weldability is improved.
The Ni-containing layer only needs to contain nickel, and examples thereof include a Ni plating layer and a Ni—Fe alloy layer.
The method for applying the Ni-containing layer to the steel plate is not particularly limited, and examples thereof include known methods such as electroplating. Also, when a Ni-Fe alloy layer is applied as the Ni-containing layer, the Ni diffusion layer is coordinated to form a Ni-Fe alloy layer by annealing after applying Ni on the steel sheet surface by electroplating or the like. Can do.
The amount of Ni in the Ni-containing layer is not particularly limited, and is preferably 50 to 2000 mg / m 2 as metal Ni equivalent per one side. If it is in the above-mentioned range, it is more excellent in resistance to sulfur blackening and is advantageous in terms of cost.
（錫めっき層）
錫めっき層付き鋼板は、鋼板表面上に錫めっき層を有する。該錫めっき層は鋼板の少なくとも片面に設けられていればよく、両面に設けられていてもよい。
錫めっき層中における鋼板片面当たりのＳｎ付着量は、０．１〜１５．０ｇ／ｍ2が好ましい。Ｓｎ付着量が上記範囲内であれば、容器用鋼板の外観特性と耐食性に優れる。なかでも、これらの特性がより優れる点で、０．２〜１５．０ｇ／ｍ2が好ましく、加工性がより優れる点で、１．０〜１５．０ｇ／ｍ2がさらに好ましい。
(Tin plating layer)
The steel plate with a tin plating layer has a tin plating layer on the steel plate surface. The tin plating layer only needs to be provided on at least one side of the steel plate, and may be provided on both sides.
The Sn adhesion amount per one surface of the steel sheet in the tin plating layer is preferably 0.1 to 15.0 g / m 2 . When the Sn adhesion amount is within the above range, the outer appearance characteristics and corrosion resistance of the steel plate for containers are excellent. Especially, 0.2-15.0 g / m < 2 > is preferable at the point which these characteristics are more excellent, and 1.0-15.0 g / m < 2 > is further more preferable at the point which processability is more excellent.
なお、Ｓｎ付着量は、電量法または蛍光Ｘ線により表面分析して測定することができる。蛍光Ｘ線の場合、金属Ｓｎ量既知のＳｎ付着量サンプルを用いて、金属Ｓｎ量に関する検量線をあらかじめ特定しておき、同検量線を用いて相対的に金属Ｓｎ量を特定する。 Note that the Sn adhesion amount can be measured by surface analysis using a coulometric method or fluorescent X-ray. In the case of fluorescent X-rays, a calibration curve relating to the amount of metallic Sn is specified in advance using an Sn adhesion amount sample with a known amount of metallic Sn, and the amount of metallic Sn is relatively identified using the calibration curve.
錫めっき層は、鋼板表面上の少なくとも一部を覆う層であり、連続層であってもよいし、不連続の島状であってもよい。 The tin plating layer is a layer covering at least a part on the surface of the steel plate, and may be a continuous layer or a discontinuous island shape.
錫めっき層としては、錫をめっきして得られる錫めっき層、または、錫めっき後通電加熱などにより錫を加熱溶融させ、錫めっき最下層（錫めっき／地鉄界面）にＦｅ-Ｓｎ合金層が一部形成した錫めっき層も含む。
また、錫めっき層としては、Ｎｉ含有層を表面に有する鋼板に対して錫めっきを行い、さらに通電加熱などにより錫を加熱溶融させ、錫めっき最下層（錫めっき／地鉄界面）にＦｅ−Ｓｎ−Ｎｉ合金、Ｆｅ−Ｓｎ合金層などが一部形成した錫めっき層も含む。
As the tin plating layer, a tin plating layer obtained by plating tin, or tin is heated and melted by energization heating after tin plating, and the Fe-Sn alloy layer is formed on the tin plating bottom layer (tin plating / base metal interface) Includes a tin plating layer partially formed.
In addition, as the tin plating layer, tin plating is performed on a steel sheet having a Ni-containing layer on the surface, and tin is further heated and melted by energization heating or the like, and Fe-- is added to the tin plating bottom layer (tin plating / base metal interface). It also includes a tin plating layer in which a part of Sn—Ni alloy, Fe—Sn alloy layer or the like is formed.
錫めっき層の製造方法としては、周知の方法（例えば、電気めっき法や溶融したＳｎに浸漬してめっきする方法）が挙げられる。
例えば、フェノールスルフォン酸錫めっき浴、メタンスルフォン酸錫めっき浴、またはハロゲン系錫めっき浴を用い、片面あたり付着量が所定量（例えば、２．８ｇ／ｍ2）となるように鋼板表面にＳｎを電気めっきした後、Ｓｎの融点（２３１．９℃）以上の温度でリフロー処理を行って、錫単体のめっき層の最下層にＦｅ−Ｓｎ合金層を形成した錫めっき層を製造できる。リフロー処理は省略した場合、錫単体のめっき層を製造できる。
As a manufacturing method of a tin plating layer, a known method (for example, an electroplating method or a method of plating by immersing in molten Sn) may be mentioned.
For example, a phenol sulfonate tin plating bath, a methane sulfonate tin plating bath, or a halogen-based tin plating bath is used, and Sn is applied to the surface of the steel sheet so that the adhesion amount per side becomes a predetermined amount (for example, 2.8 g / m 2 ). After electroplating, a reflow process is performed at a temperature equal to or higher than the melting point of Sn (231.9 ° C.), and a tin plating layer in which an Fe—Sn alloy layer is formed in the lowermost layer of the tin plating layer can be manufactured. When the reflow process is omitted, a tin plating layer can be produced.
また、鋼板がその表面上にＮｉ含有層を有する場合、Ｎｉ含有層上に錫めっき層を形成させ、リフロー処理を行うと、錫単体のめっき層の最下層（錫めっき／鋼板界面）にＦｅ-Ｓｎ−Ｎｉ合金層、Ｆｅ−Ｓｎ合金層などが形成される。 Also, when the steel sheet has a Ni-containing layer on its surface, a tin plating layer is formed on the Ni-containing layer, and when reflow treatment is performed, the lowermost layer (tin plating / steel sheet interface) of the tin simple plating layer is Fe. -Sn-Ni alloy layer, Fe-Sn alloy layer, etc. are formed.
＜皮膜＞
皮膜は、上述した錫めっき層付き鋼板の錫めっき層側の表面上に配置される。
皮膜は、その成分として、Ｚｒ（ジルコニウム元素）およびＴｉ（チタニウム元素）を含有する。さらに、皮膜は、錫めっき層付き鋼板の片面あたりのＺｒ換算の付着量（以下、「Ｚｒ付着量」ともいう）が１．０〜４０．０ｍｇ／ｍ2であり、錫めっき層付き鋼板の片面あたりのＴｉ換算の付着量（以下、「Ｔｉ付着量」ともいう）が０．０１ｍｇ／ｍ2以上８．０ｍｇ／ｍ2未満であり、皮膜のＴｉとＺｒとの質量比（Ｔｉ／Ｚｒ）が０．０１以上０．２０未満である。
<Film>
A film | membrane is arrange | positioned on the surface by the side of the tin plating layer of the steel plate with a tin plating layer mentioned above.
The coating contains Zr (zirconium element) and Ti (titanium element) as its components. Further, the coating has a Zr equivalent adhesion amount (hereinafter also referred to as “Zr adhesion amount”) of 1.0 to 40.0 mg / m 2 per one side of the steel sheet with the tin plating layer, The adhesion amount in terms of Ti per side (hereinafter also referred to as “Ti adhesion amount”) is 0.01 mg / m 2 or more and less than 8.0 mg / m 2 , and the mass ratio of Ti and Zr of the coating (Ti / Zr) ) Is 0.01 or more and less than 0.20.
上記Ｚｒ付着量が１．０ｍｇ／ｍ2未満または４０．０ｍｇ／ｍ2超である場合は、樹脂密着性および耐変色性が劣るが、１．０〜４０．０ｍｇ／ｍ2であれば樹脂密着性および耐変色性に優れ、これらの特性がより優れるという理由から、５．０〜２５．０ｍｇ／ｍ2であるのが好ましく、９．０〜２２．０ｍｇ／ｍ2であるのがより好ましい。 If the Zr coating weight of 1.0 mg / m 2 or less than 40.0 mg / m 2 than is the resin adhesion and tarnish resistance is poor, the resin if 1.0~40.0mg / m 2 It is preferably 5.0 to 25.0 mg / m 2 , more preferably 9.0 to 22.0 mg / m 2 , because of excellent adhesion and discoloration resistance and better properties. preferable.
上記Ｔｉ付着量が０．０１ｍｇ／ｍ2未満または８．０ｍｇ／ｍ2以上である場合は、樹脂密着性および耐変色性が劣るが、０．０１ｍｇ／ｍ2以上８．０ｍｇ／ｍ2未満であれば樹脂密着性および耐変色性に優れ、これらの特性がより優れるという理由から、０．０１ｍｇ／ｍ2超２．５０ｍｇ／ｍ2未満であるのが好ましく、１．８０ｍｇ／ｍ2以下であるのがより好ましく、１．５ｍｇ／ｍ2未満であるのがさらに好ましく、０．０５〜１．３ｍｇ／ｍ2が特に好ましい。 When the amount of Ti adhesion is less than 0.01 mg / m 2 or 8.0 mg / m 2 or more, the resin adhesion and discoloration resistance are inferior, but 0.01 mg / m 2 or more and less than 8.0 mg / m 2 excellent resin adhesion and tarnish resistance if the reason that these characteristics more excellent, preferably less than 0.01 mg / m 2 ultra 2.50mg / m 2, 1.80mg / m 2 or less and more preferably at, more preferably less than 1.5mg / m 2, 0.05~1.3mg / m 2 is particularly preferred.
さらに、上記質量比（Ｔｉ／Ｚｒ）が、０．０１未満である場合は樹脂密着性が劣り、０．２０以上である場合は耐変色性に劣るが、０．０１以上０．２０未満であれば、樹脂密着性および耐変色性がともに優れ、これらの特性がより優れるという理由から、０．０４〜０．１８が好ましく、０．０５〜０．１１がより好ましい。 Further, when the mass ratio (Ti / Zr) is less than 0.01, the resin adhesion is inferior, and when it is 0.20 or more, the discoloration resistance is inferior, but is 0.01 or more and less than 0.20. If it exists, 0.04-0.18 is preferable and 0.05-0.11 are more preferable from the reason that both resin adhesiveness and discoloration resistance are excellent and these characteristics are more excellent.
また、皮膜の最表面（鋼板側とは反対側の最表面）におけるＴｉとＺｒとの原子比（Ｔｉ／Ｚｒ）は、０．０５以上であると極めて優れた樹脂密着性が得られ、０．４０未満であれば極めて優れた耐変色性が得られることから、０．０５以上０．４０未満であることが好ましく、０．０７〜０．２０であるのがより好ましく、０．０９〜０．１４であるのがさらに好ましい。 Further, when the atomic ratio (Ti / Zr) of Ti and Zr on the outermost surface of the film (the outermost surface opposite to the steel plate side) is 0.05 or more, extremely excellent resin adhesion is obtained. If it is less than .40, extremely excellent discoloration resistance is obtained, it is preferably 0.05 or more and less than 0.40, more preferably 0.07 to 0.20, and 0.09 to More preferably, it is 0.14.
さらに、皮膜は、Ｐ（リン元素）を含有していてもよい。この場合、リン量（皮膜中におけるＰ量）は、より優れた耐変色性が得られるという理由から、１０．０ｍｇ／ｍ2以下が好ましく、０．１０〜１０．００ｍｇ／ｍ2がより好ましく、１．００〜５．００ｍｇ／ｍ2がさらに好ましい。
皮膜がＰを含有する場合、皮膜の最表面（鋼板側とは反対側の最表面）におけるＰとＺｒとの原子比（Ｐ／Ｚｒ）は、耐変色性がより優れるという理由から、０．３〜０．６が好ましい。
Furthermore, the film may contain P (phosphorus element). In this case, (P amount in the coating in) phosphorus amount, for the reason that better color fastness is obtained, preferably from 10.0 mg / m 2 or less, more preferably 0.10~10.00mg / m 2 1.00 to 5.00 mg / m 2 is more preferable.
When the film contains P, the atomic ratio (P / Zr) of P and Zr on the outermost surface of the film (the outermost surface opposite to the steel plate side) is 0. 3-0.6 are preferred.
なお、上述した原子比は、ＸＰＳ分析によってＺｒ３ｄ、Ｔｉ３ｄ、Ｐ２ｐのピークを分析解析して求められる。
ＸＰＳ分析としては、例えば、以下のような条件が挙げられる。
装置： 島津／ＫＲＡＴＯＳ社製 ＡＸＩＳ−ＨＳ
Ｘ線源： モノクロ ＡｌＫα線(ｈｖ＝１４８６．６ｅＶ)
測定領域： Ｈｙｂｒｉｄモード ２５０×５００（μｍ）
In addition, the atomic ratio mentioned above is calculated | required by analyzing and analyzing the peak of Zr3d, Ti3d, and P2p by XPS analysis.
Examples of XPS analysis include the following conditions.
Equipment: Shimadzu / Kratos AXIS-HS
X-ray source: Monochrome AlKα ray (hv = 14866.6 eV)
Measurement area: Hybrid mode 250 × 500 (μm)
また、皮膜中、フッ素量（皮膜中におけるＦ量）は、より優れた樹脂密着性および耐変色性が得られるという理由から、０．２ｍｇ／ｍ2未満が好ましく、０．１ｍｇ／ｍ2未満がより好ましく、０．０７ｍｇ／ｍ2未満がさらに好ましく、０．０５ｍｇ／ｍ2未満が特に好ましい。 Further, in the film, the fluorine amount (F amount in the film) is preferably less than 0.2 mg / m 2 and more preferably less than 0.1 mg / m 2 because more excellent resin adhesion and discoloration resistance can be obtained. Is more preferable, less than 0.07 mg / m 2 is more preferable, and less than 0.05 mg / m 2 is particularly preferable.
上述したＺｒ付着量、Ｔｉ付着量、およびリン量は、蛍光Ｘ線による表面分析により測定することができる。
フッ素量は、ＸＰＳ分析により皮膜の最表面におけるＺｒとＦとの原子比を測定し、上記の蛍光Ｘ線による表面分析で測定したＺｒ付着量を基に算出することができる。
The Zr adhesion amount, Ti adhesion amount, and phosphorus amount described above can be measured by surface analysis using fluorescent X-rays.
The fluorine amount can be calculated based on the Zr adhesion amount measured by the surface analysis using the fluorescent X-ray by measuring the atomic ratio of Zr and F on the outermost surface of the coating by XPS analysis.
なお、皮膜中のＺｒ、Ｔｉ、Ｐ等は、それぞれ、各種のジルコニウム化合物、チタン化合物、リン酸化合物として含まれ、これら化合物の種類や態様は特に限定されない。 In addition, Zr, Ti, P, etc. in the film are included as various zirconium compounds, titanium compounds, and phosphoric acid compounds, respectively, and the types and modes of these compounds are not particularly limited.
そして、本発明では、皮膜の赤外線吸収（ＩＲ）スペクトルにおいて、波数１５５０〜１８００ｃｍ-1の範囲に、カルボニル基（Ｃ＝Ｏ）に由来する吸収ピークを示す。すなわち、皮膜中にカルボニル基が含まれる。これにより、本発明の容器用鋼板は、樹脂密着性および耐変色性に優れる。なお、皮膜中に含まれるカルボニル基は、後述する処理液に含まれるオキシ酢酸ジルコニウム（酢酸ジルコニル）〔ＺｒＯ（ＣＨ3ＣＯＯ）2〕に由来するものと考えられる。 And in this invention, the absorption peak derived from a carbonyl group (C = O) is shown in the range of wave numbers 1550-1800 cm < -1 > in the infrared absorption (IR) spectrum of a film | membrane. That is, a carbonyl group is contained in the film. Thereby, the steel plate for containers of this invention is excellent in resin adhesiveness and discoloration resistance. Incidentally, a carbonyl group contained in the coating is considered to be originated from the zirconium oxyacetate included in the processing solution described below (zirconyl acetate) [ZrO (CH 3 COO) 2].
赤外線吸収（ＩＲ）スペクトルの測定条件は、例えば以下のものが挙げられる。
装置： Ｖａｒｉａｎ製 ＦＴＳ−３１００
測定方法： ＡＴＲ／ＧＥプリズム
分解能： ４ｃｍ-1
積算回数： ３２回
Examples of the measurement conditions of the infrared absorption (IR) spectrum include the following.
Apparatus: FTS-3100 manufactured by Varian
Measuring method: ATR / GE prism Resolution: 4 cm -1
Integration count: 32 times
皮膜中に含まれるカルボニル基の量は、皮膜中のＺｒ１モルに対して０．６モル以上１．２モル未満が好ましい。上述したように、皮膜中のカルボニル基によって皮膜表面の親水性が低下するが、この量が１．２モル以上であると過多に疎水性となり容器用鋼板の樹脂密着性を損なう場合がある。また、０．６モル未満であっても樹脂密着性が不十分となる場合がある。
しかし、皮膜中に含まれるカルボニル基の量が上記範囲内であれば、容器用鋼板の樹脂密着性がより優れる。
The amount of the carbonyl group contained in the film is preferably 0.6 mol or more and less than 1.2 mol with respect to 1 mol of Zr in the film. As described above, the hydrophilicity of the film surface is lowered by the carbonyl group in the film, but if this amount is 1.2 mol or more, it becomes excessively hydrophobic and may impair the resin adhesion of the steel plate for containers. Moreover, even if it is less than 0.6 mol, resin adhesiveness may become inadequate.
However, if the amount of the carbonyl group contained in the film is within the above range, the resin adhesion of the steel plate for containers is more excellent.
このようなカルボニル基の量は、次のように求める。まず、ＸＰＳ分析のワイドスキャンによって各元素（Ｃ、Ｏ、Ｚｒ、Ｓｎ、Ｔｉ、他）の組成率（原子％）を算出する。次に、Ｃ１Ｓのナロ−ピークを解析し、（ア）２８５．０±０．３ｅＶ、（イ）２８６．５±０．３ｅＶ、（ウ）８９．０±０．３ｅＶの３波に分離する。ここで、この３波の各ピークはそれぞれ、（ア）：Ｃ−ＣまたはＣ−Ｈ、（イ）：Ｃ−ＯまたはＣ−ＯＨ、（ウ）：Ｃ（＝Ｏ）Ｏ−（カルボニル基）に対応する。分離した３つのピークについて面積を算出し、（ウ）：カルボニル基の存在比率を計算する。Ｃ組成率（原子％）にカルボニル基の存在比率を乗じ、カルボニル基の量（組成率、原子％）を求める。求めたカルボニル基の量とＺｒの組成率とから、Ｚｒ１モルに対するカルボニル基のモル量を求める。
ＸＰＳ分析としては、例えば、以下のような条件が挙げられる。
・装置：島津／ＫＲＡＴＯＳ社製 ＡＸＩＳ−ＨＳ
・Ｘ線源：モノクロ ＡｌＫα線(ｈｖ＝１４８６．６ｅＶ)
・測定領域：Ｈｙｂｒｉｄモード ２５０×５００（μｍ）
The amount of such a carbonyl group is determined as follows. First, the composition ratio (atomic%) of each element (C, O, Zr, Sn, Ti, etc.) is calculated by XPS analysis wide scan. Next, the N1 peak of C1S is analyzed and separated into three waves (a) 285.0 ± 0.3 eV, (b) 286.5 ± 0.3 eV, and (c) 89.0 ± 0.3 eV. . Here, each peak of the three waves is (a): C—C or C—H, (A): C—O or C—OH, (U): C (═O) O— (carbonyl group). ). The area is calculated for the three separated peaks, and (U): the abundance ratio of the carbonyl group is calculated. The amount of carbonyl groups (composition ratio, atomic%) is determined by multiplying the C composition ratio (atomic%) by the abundance ratio of carbonyl groups. From the obtained amount of carbonyl group and the composition ratio of Zr, the molar amount of the carbonyl group relative to 1 mol of Zr is obtained.
Examples of XPS analysis include the following conditions.
・ Equipment: Shimazu / KRATOS AXIS-HS
X-ray source: Monochrome AlKα ray (hv = 1486.6 eV)
・ Measurement area: Hybrid mode 250 × 500 (μm)
〔容器用鋼板の製造方法、処理液〕
上述した本発明の容器用鋼板を製造する方法としては、特に限定されないが、後述する処理液（以下、「本発明の処理液」ともいう）中に錫めっき層付き鋼板を浸漬する、または、本発明の処理液中に浸漬した錫めっき層付き鋼板に陰極電解処理を施すことにより、上述した皮膜を形成する皮膜形成工程を少なくとも備える方法（以下、「本発明の製造方法」ともいう）であるのが好ましい。
以下、本発明の製造方法について説明を行い、この説明の中で、併せて本発明の処理液についても説明する。
[Manufacturing method and processing solution for steel plate for containers]
The method for producing the container steel plate of the present invention described above is not particularly limited, but the steel plate with a tin plating layer is immersed in a treatment liquid described below (hereinafter, also referred to as “treatment liquid of the present invention”), or By a method (hereinafter also referred to as “production method of the present invention”) including at least a film forming step of forming the above-described film by subjecting a steel sheet with a tin plating layer immersed in the treatment liquid of the present invention to cathodic electrolysis. Preferably there is.
Hereinafter, the production method of the present invention will be described, and in this description, the treatment liquid of the present invention will also be described.
＜皮膜形成工程＞
皮膜形成工程は、錫めっき層付き鋼板の錫めっき層側の表面上に、上述した皮膜を形成する工程であって、後述する本発明の処理液中に錫めっき層付き鋼板を浸漬する（浸漬処理）、または、浸漬した鋼板に陰極電解処理を施す工程である。陰極電解処理は、浸漬処理よりも、より高速に、均一な皮膜を得ることができるという理由から好ましい。なお、陰極電解処理と陽極電解処理とを交互に行う交番電解を実施してもよい。
以下に、使用される本発明の処理液、陰極電解処理の条件などについて詳述する。
<Film formation process>
The film forming step is a step of forming the above-described film on the surface on the tin plating layer side of the steel plate with the tin plating layer, and immersing the steel plate with the tin plating layer in the treatment liquid of the present invention described later (immersion) Treatment), or a step of subjecting the immersed steel plate to cathodic electrolysis. Cathodic electrolytic treatment is preferable because a uniform film can be obtained at a higher speed than immersion treatment. In addition, you may implement the alternating electrolysis which performs a cathode electrolytic treatment and an anodic electrolytic treatment alternately.
Hereinafter, the treatment liquid of the present invention used, conditions for the cathodic electrolysis, and the like will be described in detail.
（本発明の処理液）
本発明の処理液は、Ｚｒ（ジルコニウム元素）およびＴｉ（チタニウム元素）を含有する上記皮膜を形成するためのものであり、Ｚｒの供給源として、オキシ酢酸ジルコニウムを含有し、Ｔｉの供給源として、チタン化合物を含有する。
本発明の処理液がオキシ酢酸ジルコニウムを含有することで、形成される皮膜はカルボニル基を有する。また、ジルコンフッ化カリウム等のフッ素系のジルコニウム供給源が不使用となるため、皮膜中のフッ素量が低減される。なお、皮膜中におけるカルボニル基の存在およびフッ素量低減の効果については、上述したとおりである。
(Processing liquid of the present invention)
The treatment liquid of the present invention is for forming the above film containing Zr (zirconium element) and Ti (titanium element), and contains zirconium oxyacetate as a supply source of Zr and as a supply source of Ti. And a titanium compound.
Since the treatment liquid of the present invention contains zirconium oxyacetate, the formed film has a carbonyl group. Moreover, since a fluorine-based zirconium supply source such as zircon potassium fluoride is not used, the amount of fluorine in the film is reduced. The presence of the carbonyl group in the film and the effect of reducing the amount of fluorine are as described above.
オキシ酢酸ジルコニウム〔ＺｒＯ（ＣＨ3ＣＯＯ）2〕は、酢酸ジルコニルとも呼ばれるものであり、本発明の処理液における含有量は、０．３〜１５．０ｇ／Ｌが好ましく、３．０〜９．０ｇ／Ｌがより好ましい。 Zirconium oxyacetate [ZrO (CH 3 COO) 2 ] is also called zirconyl acetate, and the content in the treatment liquid of the present invention is preferably 0.3 to 15.0 g / L, and preferably 3.0 to 9. 0 g / L is more preferable.
チタン化合物としては、例えば、チタンフッ化水素酸および／またはその塩、ならびに、シュウ酸チタニルアンモニウム、チタンアルコキシド、シュウ酸チタニルカリウム２水和物、硫酸チタンなどの水溶性チタン化合物等を用いることができる。
チタンフッ化水素酸〔Ｈ2ＴｉＦ6〕は、フッ化チタン酸とも呼ばれる。また、チタンフッ化水素酸の塩としては、例えば、チタンフッ化カリウム〔Ｋ2ＴｉＦ6〕、チタンフッ化アンモニウム〔（ＮＨ4）2ＴｉＦ6〕、チタンフッ化ソーダ〔Ｎａ2ＴｉＦ6〕等が挙げられる。
本発明の処理液におけるチタン化合物の含有量としては、２×１０-5〜１×１０-3ｍｏｌ／Ｌが好ましく、３×１０-4〜５×１０-4ｍｏｌ／Ｌがより好ましい。
Examples of the titanium compound include titanium hydrofluoric acid and / or a salt thereof, and water-soluble titanium compounds such as titanyl ammonium oxalate, titanium alkoxide, titanyl potassium oxalate dihydrate, titanium sulfate, and the like. .
Titanium hydrofluoric acid [H 2 TiF 6 ] is also called fluorinated titanic acid. Examples of the salt of titanium hydrofluoric acid include titanium potassium fluoride [K 2 TiF 6 ], titanium ammonium fluoride [(NH 4 ) 2 TiF 6 ], and titanium fluoride fluoride [Na 2 TiF 6 ].
The content of the titanium compound in the treatment liquid of the present invention is preferably 2 × 10 −5 to 1 × 10 −3 mol / L, and more preferably 3 × 10 −4 to 5 × 10 −4 mol / L.
また、上記皮膜がＰ（リン元素）を含む場合、本発明の処理液にはＰ供給源が含まれ、このＰ供給源としては、例えば、リン酸（オルトリン酸）、リン酸Ｎａ、リン酸水素ナトリウム、第１リン酸アルミニウム、第１リン酸マグネシウム、第１リン酸カルシウムなどのリン酸および／またはその塩が挙げられ、含有量としては、０．０１〜５．０ｇ／Ｌが好ましく、０．０２〜０．０５ｇ／Ｌがより好ましい。 When the above film contains P (phosphorus element), the treatment liquid of the present invention contains a P supply source. Examples of the P supply source include phosphoric acid (orthophosphoric acid), phosphoric acid Na, and phosphoric acid. Examples thereof include phosphoric acid and / or a salt thereof such as sodium hydrogen, primary aluminum phosphate, primary magnesium phosphate, primary calcium phosphate, and the content is preferably 0.01 to 5.0 g / L. 02 to 0.05 g / L is more preferable.
さらに、本発明の処理液は、電導助剤を含むのが好ましく、具体的には、上記電導助剤として、硝酸イオンである陰イオンと、カリウムイオン、アンモニウムイオンおよびナトリウムイオンからなる群から選ばれる少なくとも１種の陽イオンと、を含有するのが好ましい。
本発明の処理液が上記電導助剤を含むことにより、上記皮膜を形成できるラインスピードを高速化できる。すなわち、高速操業性に優れる。これは、電導助剤を含むことにより、処理液の電気伝導性すなわち液抵抗が低下・改善し、高速化に伴う高電流を通電することが容易になるためと考えられる。具体的には、鋼板の片面あたりにおけるＺｒ換算の付着量が１５ｍｇ／ｍ2となるように３００ｍ／分のラインスピードで陰極電解処理を行うときの鋼板と電極間とに印加される電位差が２０Ｖ未満となるような電気伝導度となる処理液であれば、通常の皮膜形成工程ラインに設置される整流器を用いることが可能となり、高速操業が可能となるので、好ましい。
上記電導助剤は、実質的には、上記陰イオンと上記陽イオンとがイオン結合した塩として、本発明の処理液に含まれ、その含有量としては、高速操業性がより優れるという理由から、０．１〜１０．０ｇ／Ｌが好ましく、０．５〜５．０ｇ／Ｌがより好ましい。
Furthermore, the treatment liquid of the present invention preferably contains a conductive aid. Specifically, the conductive aid is selected from the group consisting of anions which are nitrate ions, potassium ions, ammonium ions and sodium ions. And at least one cation.
When the treatment liquid of the present invention contains the conductive aid, the line speed at which the film can be formed can be increased. That is, it is excellent in high-speed operability. This is presumably because the electrical conductivity of the treatment liquid, that is, the liquid resistance is reduced and improved by including the conductive auxiliary agent, and it becomes easy to pass a high current accompanying the increase in speed. Specifically, the potential difference applied between the steel plate and the electrode when the cathodic electrolysis is performed at a line speed of 300 m / min so that the amount of Zr equivalent adhesion per side of the steel plate is 15 mg / m 2 is 20 V. A treatment liquid having an electrical conductivity that is less than 5 is preferable because a rectifier installed in a normal film forming process line can be used and high-speed operation is possible.
The conductive assistant is substantially contained in the treatment liquid of the present invention as a salt in which the anion and the cation are ion-bonded, and the content thereof is more excellent in high-speed operability. 0.1 to 10.0 g / L is preferable, and 0.5 to 5.0 g / L is more preferable.
なお、本発明の処理液中の溶媒としては、通常水が使用されるが、有機溶媒を併用してもよい。 In addition, although water is normally used as a solvent in the processing liquid of this invention, you may use an organic solvent together.
本発明の処理液のｐＨは、特に限定されないが、ｐＨ２．０〜５．０が好ましい。該範囲内であれば、処理時間を短くすることができ、かつ、処理液の安定性に優れる。
ｐＨの調整には公知の酸成分（例えば、リン酸、硫酸）・アルカリ成分（例えば、水酸化ナトリウム、アンモニア水）を使用することができる。
Although the pH of the processing liquid of this invention is not specifically limited, pH 2.0-5.0 are preferable. Within this range, the treatment time can be shortened and the stability of the treatment liquid is excellent.
A known acid component (for example, phosphoric acid, sulfuric acid) / alkali component (for example, sodium hydroxide, aqueous ammonia) can be used to adjust the pH.
本発明の処理液には、必要に応じて、ラウリル硫酸ナトリウム、アセチレングリコールなどの界面活性剤が含まれていてもよい。また、付着挙動の経時的な安定性の観点から、処理液には、ピロリン酸塩などの縮合リン酸塩が含まれていてもよい。 The treatment liquid of the present invention may contain a surfactant such as sodium lauryl sulfate or acetylene glycol as necessary. Further, from the viewpoint of the stability of the adhesion behavior over time, the treatment liquid may contain a condensed phosphate such as pyrophosphate.
再び皮膜形成工程の説明に戻る。皮膜形成行程において、処理を実施する際の処理液の液温は、皮膜の形成効率、組織の均一性により優れ、かつ、低コストの点から、２０〜８０℃が好ましく、４０〜６０℃がより好ましい。 Returning to the description of the film forming process again. In the film formation process, the liquid temperature of the treatment liquid at the time of performing the treatment is preferably 20 to 80 ° C., and preferably 40 to 60 ° C. from the viewpoint of film formation efficiency and tissue uniformity and low cost. More preferred.
皮膜形成工程において、陰極電解処理を実施する際の電解電流密度は、形成される皮膜の樹脂密着性および耐変色性がより優れるという理由から、低電流密度であることが好ましく、より具体的には、０．０５〜７．０Ａ／ｄｍ2が好ましく、１．０〜２．０Ａ／ｄｍ2がより好ましい。本発明の処理液を用いることにより、低電流密度での皮膜の形成が可能となる。 In the film formation step, the electrolysis current density at the time of carrying out the cathodic electrolysis treatment is preferably a low current density from the reason that the resin adhesion and discoloration resistance of the film to be formed are more excellent. is preferably 0.05~7.0A / dm 2, 1.0~2.0A / dm 2 is more preferable. By using the treatment liquid of the present invention, a film can be formed at a low current density.
このとき、陰極電解処理の通電時間は、付着量低下がより抑制されて安定的に皮膜の形成ができ、形成された皮膜の特性低下がより抑制される点から、０．１〜５秒が好ましく、０．３〜２秒がより好ましい。
また、陰極電解処理の際の電気量密度は、０．２０〜３．５０Ｃ／ｄｍ2が好ましく、０．４０〜２．００Ｃ／ｄｍ2がより好ましい。
At this time, the energization time of the cathodic electrolysis treatment is 0.1 to 5 seconds from the point that the decrease in the adhesion amount is further suppressed and the film can be stably formed, and the characteristic deterioration of the formed film is further suppressed. Preferably, 0.3 to 2 seconds is more preferable.
Moreover, 0.20 to 3.50 C / dm < 2 > is preferable and, as for the electric quantity density in the case of cathodic electrolysis processing, 0.40 to 2.00 C / dm < 2 > is more preferable.
なお、陰極電解処理の後、必要に応じて、未反応物を除去するため、得られた鋼板の水洗処理および／または乾燥を行ってもよい。なお、乾燥の際の温度および方式については特に限定されず、例えば、通常のドライヤーや電気炉乾燥方式が適用できる。
なお、乾燥処理の際の温度としては、１００℃以下が好ましい。上記範囲内であれば、皮膜の酸化を抑制することができ、皮膜組成の安定性が保たれる。なお、下限は特に限定されないが、通常室温程度である。
In addition, in order to remove an unreacted substance after a cathode electrolytic treatment, you may perform the water-washing process and / or drying of the obtained steel plate as needed. In addition, it does not specifically limit about the temperature and system in the case of drying, For example, a normal dryer and an electric furnace drying system are applicable.
In addition, as temperature in the case of a drying process, 100 degrees C or less is preferable. If it is in the said range, the oxidation of a film | membrane can be suppressed and stability of a film | membrane composition is maintained. The lower limit is not particularly limited, but is usually about room temperature.
＜前処理工程＞
本発明の製造方法は、上述した皮膜形成工程の前に、以下に説明する前処理工程を備えていてもよい。
前処理工程は、アルカリ性水溶液（特に、炭酸ナトリウム水溶液）中で錫めっき層付き鋼板に陰極電解処理を施す工程である。
通常、錫めっき層の作製時にその表面は酸化されて、錫酸化物が形成される。該鋼板に対して、陰極電解処理を施すことにより、不要な錫酸化物を除去して、錫酸化物量を調整できる。
前処理工程の陰極電解処理の際に使用される溶液としては、アルカリ性水溶液（例えば、炭酸ナトリウム水溶液）が挙げられる。アルカリ性水溶液中のアルカリ成分（例えば、炭酸ナトリウム）の濃度は特に制限されないが、錫酸化物の除去がより効率的に進行する点から、５〜１５ｇ／Ｌが好ましく、８〜１２ｇ／Ｌがより好ましい。
陰極電解処理の際のアルカリ性水溶液の液温は特に制限されないが、４０〜６０℃が好ましい。陰極電解処理の電解条件（電流密度、電解時間）は、適宜調整される。なお、陰極電解処理の後に、必要に応じて、水洗処理を施してもよい。
<Pretreatment process>
The manufacturing method of this invention may be equipped with the pre-processing process demonstrated below before the film formation process mentioned above.
The pretreatment step is a step of subjecting the steel plate with the tin plating layer to cathodic electrolysis in an alkaline aqueous solution (particularly, an aqueous sodium carbonate solution).
Usually, the surface of the tin-plated layer is oxidized to form tin oxide. By subjecting the steel plate to cathodic electrolysis, unnecessary tin oxide can be removed and the amount of tin oxide can be adjusted.
Examples of the solution used for the cathodic electrolysis in the pretreatment step include an alkaline aqueous solution (for example, an aqueous sodium carbonate solution). The concentration of the alkaline component (for example, sodium carbonate) in the alkaline aqueous solution is not particularly limited, but is preferably 5 to 15 g / L, more preferably 8 to 12 g / L from the viewpoint that removal of tin oxide proceeds more efficiently. preferable.
The temperature of the alkaline aqueous solution during the cathodic electrolysis is not particularly limited, but is preferably 40 to 60 ° C. The electrolysis conditions (current density, electrolysis time) of the cathodic electrolysis are appropriately adjusted. In addition, you may perform a water washing process after a cathode electrolytic process as needed.
本発明の製造方法によって得られた本発明の容器用鋼板は、ＤＩ缶、食缶、飲料缶など種々の容器の製造に使用される。 The steel plate for containers of the present invention obtained by the manufacturing method of the present invention is used for manufacturing various containers such as DI cans, food cans and beverage cans.
以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
＜錫めっき層付き鋼板の製造＞
以下の２つの方法［（Ｋ−１）および（Ｋ−２）］によって、錫めっき層付き鋼板を製造した。
（Ｋ−１）
板厚０．２２ｍｍの鋼板（Ｔ４原板）について電解脱脂と酸洗を行い、その後錫めっきを施した。引き続き、錫の融点以上の温度で加熱溶融処理し、第３表に示す片面当たりのＳｎ付着量の錫めっき層をＴ４原板の両面に形成した。
（Ｋ−２）
板厚０．２２ｍｍの鋼板（Ｔ４原板）を電解脱脂し、ワット浴を用いて第３表に示す片面当たりのＮｉ付着量でニッケルめっき層を両面に形成後、１０ｖｏｌ.％Ｈ2＋９０ｖｏｌ.％Ｎ2雰囲気中にて７００℃で焼鈍してニッケルめっきを拡散浸透させることによりＦｅ−Ｎｉ合金層（Ｎｉ含有層）（第３表にＮｉ付着量を示す）を両面に形成した。
引き続き、上記表層にＮｉ含有層を有する鋼板を、錫めっき浴を用い、第３表中に示す片面当たりのＳｎ付着量でＳｎ層を両面に形成後、Ｓｎの融点以上でリフロー処理を施し、錫めっき層をＴ４原板の両面に形成した。
<Manufacture of steel sheet with tin plating layer>
A steel plate with a tin plating layer was produced by the following two methods [(K-1) and (K-2)].
(K-1)
Electrolytic degreasing and pickling were performed on a steel plate (T4 original plate) having a thickness of 0.22 mm, and then tin plating was performed. Subsequently, it was heated and melted at a temperature equal to or higher than the melting point of tin, and a tin plating layer having an Sn adhesion amount per one side shown in Table 3 was formed on both sides of the T4 original plate.
(K-2)
A steel plate (T4 original plate) having a thickness of 0.22 mm was electrolytically degreased and a nickel plating layer was formed on both sides with a Ni adhesion amount per one side shown in Table 3 using a Watt bath, and then 10 vol.% H 2 +90 vol.% An Fe—Ni alloy layer (Ni-containing layer) (showing Ni adhesion amount in Table 3) was formed on both surfaces by annealing at 700 ° C. in an N 2 atmosphere to diffuse and infiltrate nickel plating.
Subsequently, a steel plate having a Ni-containing layer as the surface layer was formed using a tin plating bath, Sn layers were formed on both sides with the Sn adhesion amount per one side shown in Table 3, and a reflow treatment was performed at a melting point of Sn or higher. Tin plating layers were formed on both sides of the T4 original plate.
＜皮膜の形成＞
浴温５０℃、１０ｇ／Ｌの炭酸ナトリウム水溶液中に錫めっき層付き鋼板を浸漬し、第２表に示す条件にて、陰極電解処理を行った（前処理工程）。
その後、得られた鋼板を水洗し、第１表に示す組成およびｐＨの処理液（溶媒：水）を用い、第２表に示す浴温、電解条件（電流密度、通電時間、電気量密度）で陰極電解処理を施した。その後、得られた鋼板を水洗して、ブロアを用いて室温で乾燥を行い、皮膜を両面に形成した（皮膜形成工程）。
発明例１〜３４および比較例１〜１０においては、皮膜形成工程を実験室で処理し、第３表に示す皮膜を形成した。
<Formation of film>
A steel plate with a tin plating layer was immersed in an aqueous sodium carbonate solution having a bath temperature of 50 ° C. and 10 g / L, and cathodic electrolysis was performed under the conditions shown in Table 2 (pretreatment step).
Thereafter, the obtained steel sheet was washed with water, and using the treatment liquid (solvent: water) having the composition and pH shown in Table 1, the bath temperature and electrolysis conditions (current density, energization time, electric quantity density) shown in Table 2 were used. Was subjected to cathodic electrolysis. Then, the obtained steel plate was washed with water, dried at room temperature using a blower, and a film was formed on both sides (film formation process).
In Invention Examples 1 to 34 and Comparative Examples 1 to 10, the film formation step was processed in the laboratory to form the films shown in Table 3.
作製した鋼板に対して、以下の方法で、樹脂密着性および耐変色性を評価した。各成分量、および、評価結果を第３表にまとめて示す。
皮膜のＺｒ付着量、Ｔｉ付着量、リン量（Ｐ量）、フッ素量（Ｆ量）、各種原子比、は、上述の方法により測定した。また、赤外線吸収（ＩＲ）スペクトルを測定し、波数１５５０〜１８００ｃｍ-1の範囲に、カルボニル基（Ｃ＝Ｏ）に由来する吸収ピークが存在するかどうかを確認した。さらに、上述した方法により、皮膜中のカルボニル基について、Ｚｒ１モルに対するモル量を求めた。
The produced steel sheet was evaluated for resin adhesion and discoloration resistance by the following methods. The amount of each component and the evaluation results are summarized in Table 3.
The Zr adhesion amount, Ti adhesion amount, phosphorus amount (P amount), fluorine amount (F amount), and various atomic ratios of the film were measured by the above-described methods. Further, an infrared absorption (IR) spectrum was measured, and it was confirmed whether or not an absorption peak derived from a carbonyl group (C═O) was present in the range of wave numbers 1550 to 1800 cm −1 . Furthermore, the molar amount with respect to Zr1 mol was calculated | required about the carbonyl group in a film | membrane by the method mentioned above.
＜高速操業性の評価）＞
一部の実施例（発明例３６〜４１）では、皮膜形成工程のラインにおいて、３００ｍ／分のラインスピードで操業を行い、鋼板の片面あたりにおけるＺｒ換算の付着量が１５ｍｇ／ｍ2となるように陰極電解処理を施した。この陰極電解処理時の鋼板と電極間とに印加される電位差を求め、次のように高速操業性を評価し、◎または○であれば高速操業性が良好であるとした。結果を第３表に示す。なお、発明例３５では３００ｍ／分のラインスピードで操業すると３０Ｖ以上の電位差となり通常の整流器では容量が不足するため、１００ｍ／分のラインスピードで操業を行い、鋼板の片面あたりにおけるＺｒ換算の付着量が１５ｍｇ／ｍ2となるように陰極電解処理を施した。
◎：鋼板と電極間との電位差が１０Ｖ未満
○：鋼板と電極間との電位差が１０Ｖ以上２０Ｖ未満
△：鋼板と電極間との電位差が２０Ｖ以上３０Ｖ未満
×：鋼板と電極間との電位差が３０Ｖ以上
なお、皮膜形成の有無は、蛍光Ｘ線により表面分析することにより判定し、鋼板の片面あたりのＺｒ換算の付着量が１．０ｍｇ／ｍ2以上、Ｔｉ換算の付着量が０．０１ｍｇ／ｍ2以上の場合に、鋼板に皮膜が形成されたものと判断した。
<Evaluation of high-speed operability>
In some Examples (Invention Examples 36 to 41), the film formation process line is operated at a line speed of 300 m / min so that the Zr equivalent adhesion amount per side of the steel sheet is 15 mg / m 2. Was subjected to cathodic electrolysis. The potential difference applied between the steel plate and the electrode during the cathodic electrolysis treatment was determined, and the high speed operability was evaluated as follows. The results are shown in Table 3. In Invention Example 35, when operating at a line speed of 300 m / min, the potential difference becomes 30 V or more, and the capacity of a normal rectifier is insufficient. Therefore, operation is performed at a line speed of 100 m / min, and Zr conversion adhesion on one side of the steel sheet. Cathodic electrolysis was performed so that the amount was 15 mg / m 2 .
A: Potential difference between the steel plate and the electrode is less than 10 V. O: Potential difference between the steel plate and the electrode is 10 V or more and less than 20 V. Δ: Potential difference between the steel plate and the electrode is 20 V or more and less than 30 V. X: Potential difference between the steel plate and the electrode. 30 V or more In addition, the presence or absence of film formation is determined by performing surface analysis with fluorescent X-rays. The amount of Zr conversion per one side of the steel sheet is 1.0 mg / m 2 or more, and the amount of Ti conversion is 0.01 mg. / M 2 or more, it was judged that a film was formed on the steel sheet.
＜樹脂密着性＞
作製した容器用鋼板の両面に、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をラミネートして、ラミネート鋼板を作製した。ラミネートは、２１０℃に加熱した鋼板とフィルムを一対のゴムロールで挟んでフィルムを鋼板に融着させ、ゴムロール通過後１ｓｅｃ以内に水冷して行った。このとき、鋼板の送り速度は４０ｍ／ｍｉｎ、ゴムロールのニップ長は１７ｍｍであった。ここで、ニップ長とは、ゴムロールと鋼板が接する部分の搬送方向の長さのことである。そして、作製したラミネート鋼板について、次の樹脂密着性の評価を行った。
樹脂密着性の評価は、温度１５０℃、相対湿度１００％のレトルト雰囲気における１８０度ピール試験により行った。１８０度ピール試験とは、図１（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）を用い、図１（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度折り返して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（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
<Resin adhesion>
A laminated steel plate was prepared by laminating an isophthalic acid copolymerized polyethylene terephthalate film having a thickness of 25 μm and a copolymerization ratio of 12 mol% on both surfaces of the produced steel plate for containers. Lamination was performed by sandwiching a steel plate and a film heated to 210 ° C. between a pair of rubber rolls, fusing the film to the steel plate, and cooling with water within 1 sec after passing through the rubber roll. At this time, the feeding speed of the steel plate was 40 m / min, and the nip length of the rubber roll was 17 mm. Here, the nip length is the length in the transport direction of the portion where the rubber roll and the steel plate are in contact. And about the produced laminated steel plate, the following resin adhesiveness evaluation was performed.
Evaluation of resin adhesion was performed by a 180 degree peel test in a retort atmosphere at a temperature of 150 ° C. and a relative humidity of 100%. The 180 degree peel test uses a test piece (size: 30 mm × 100 mm) obtained by cutting a
A: Peel length is less than 15 mm B: Peel length is 15 mm or more and less than 20 mm Δ: Peel length is 20 mm or more and less than 50 mm X: Peel length is 50 mm or more
＜耐変色性＞
作製した容器用鋼板の両面に、樹脂密着性を評価したときと同様にしてラミネートし、ラミネート鋼板を作製した。市販のトマトジュースを入れたビーカーに、ラミネート鋼板の試験片（サイズ：５０ｍｍ×１００ｍｍ）を入れ、５５℃の恒温槽に２０日間放置する試験を行った。気相部（トマトジュースに浸かっていない部分）の変色を評価した。
試験前後のラミネート鋼板のＬ値、ａ値、ｂ値をスガ試験機製カラーメーターＳＭ−Ｔで測定し、試験前後の色差を以下のように計算して求めた。
ΔＥ＝（（Ｌ試験前−Ｌ試験後）2＋（ａ試験前−ａ試験後）2＋（ｂ試験前−ｂ試験後）2）0.5
その結果、次のように耐変色性を評価し、◎または○であれば耐変色性が良好であるとした。
◎：色差が３未満
○：色差が３以上、８未満
△：色差が８以上、１５未満
×：色差が１５以上
<Discoloration resistance>
Lamination was performed on both surfaces of the produced steel plate for containers in the same manner as when the resin adhesion was evaluated to produce a laminated steel plate. A test piece (size: 50 mm × 100 mm) of a laminated steel plate was placed in a beaker containing a commercially available tomato juice, and a test was performed in a constant temperature bath at 55 ° C. for 20 days. Discoloration of the gas phase part (part not immersed in tomato juice) was evaluated.
The L value, a value, and b value of the laminated steel sheet before and after the test were measured with a color meter SM-T manufactured by Suga Test Instruments, and the color difference before and after the test was calculated as follows.
ΔE = ((before L test−after L test) 2 + (before a test−after a test) 2 + (before b test−after b test) 2 ) 0.5
As a result, the discoloration resistance was evaluated as follows, and if it was A or B, it was determined that the discoloration resistance was good.
◎: Color difference is less than 3 ○: Color difference is 3 or more, less than 8 Δ: Color difference is 8 or more, less than 15 ×: Color difference is 15 or more
上記第１〜３表に示す結果から明らかなように、本発明例はいずれも樹脂密着性および耐変色性に優れることが確認された。
これに対して、皮膜からカルボニル基に由来する吸収ピークが確認されなかった比較例１〜８は、樹脂密着性および耐変色性が劣っていた。
また、Ｔｉ付着量が８．０ｍｇ／ｍ2以上であって質量比（Ｔｉ／Ｚｒ）が０．２０以上である比較例９は、耐変色性が劣っていた。
また、質量比（Ｔｉ／Ｚｒ）が０．０１未満である比較例１０は、樹脂密着性に劣っていた。
また、電導助剤を含有する処理液を用いて皮膜を形成した発明例３６〜４１は、高速操業性が優れていた。
As is apparent from the results shown in Tables 1 to 3 above, it was confirmed that all of the inventive examples were excellent in resin adhesion and discoloration resistance.
On the other hand, Comparative Examples 1 to 8 in which absorption peaks derived from carbonyl groups were not confirmed from the film were inferior in resin adhesion and discoloration resistance.
Further, in Comparative Example 9 in which the Ti adhesion amount was 8.0 mg / m 2 or more and the mass ratio (Ti / Zr) was 0.20 or more, the discoloration resistance was inferior.
Moreover, the comparative example 10 whose mass ratio (Ti / Zr) is less than 0.01 was inferior to resin adhesiveness.
Inventive Examples 36 to 41, in which a film was formed using a treatment liquid containing a conductive assistant, were excellent in high-speed operability.
１ 容器用鋼板
２ フィルム
３ 鋼板の切り取った部位
４ 重り
５ 剥離長
DESCRIPTION OF
Claims (11)
前記皮膜が、ＺｒおよびＴｉを有し、
前記皮膜は、前記錫めっき層付き鋼板の片面あたりのＺｒ換算の付着量が１．０〜４０．０ｍｇ／ｍ2であって、前記錫めっき層付き鋼板の片面あたりのＴｉ換算の付着量が０．０１ｍｇ／ｍ2以上８．０ｍｇ／ｍ2未満であり、
前記皮膜のＴｉとＺｒとの質量比（Ｔｉ／Ｚｒ）が０．０１以上０．２０未満であり、
前記皮膜の赤外線吸収（ＩＲ）スペクトルにおいて、波数１５５０〜１８００ｃｍ-1の範囲にカルボニル基（Ｃ＝Ｏ）に由来する吸収ピークを示すことを特徴とする容器用鋼板。 A steel plate for a container comprising a steel plate and a steel plate with a tin plating layer having a tin plating layer covering at least a part of the surface of the steel plate, and a coating disposed on the surface of the steel plate with the tin plating layer on the tin plating layer side Because
The coating has Zr and Ti;
The coating has a Zr equivalent adhesion amount per side of the steel sheet with the tin plating layer of 1.0 to 40.0 mg / m 2 , and has a Ti equivalent adhesion amount per side of the steel sheet with the tin plating layer. 0.01 mg / m 2 or more and less than 8.0 mg / m 2 ,
The mass ratio (Ti / Zr) of Ti and Zr of the coating is 0.01 or more and less than 0.20,
In the infrared absorption (IR) spectrum of the film, a steel plate for containers showing an absorption peak derived from a carbonyl group (C = O) in the range of wave numbers from 1550 to 1800 cm- 1 .
オキシ酢酸ジルコニウムと、チタン化合物とを含有することを特徴とする、処理液。 It is a processing liquid used for manufacture of the steel plate for containers according to any one of claims 1 to 6,
A treatment liquid comprising zirconium oxyacetate and a titanium compound.
請求項７〜９のいずれか１項に記載の処理液中に前記錫めっき層付き鋼板を浸漬する、または、浸漬した前記錫めっき層付き鋼板に陰極電解処理を施すことにより、前記皮膜を形成することを特徴とする容器用鋼板の製造方法。 It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers given in any 1 paragraph of Claims 1-6,
The said film is formed by immersing the said steel plate with a tin plating layer in the process liquid of any one of Claims 7-9, or performing a cathodic electrolytic process to the immersed said steel plate with a tin plating layer The manufacturing method of the steel plate for containers characterized by performing.
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| WO2015012176A1 (en) * | 2013-07-24 | 2015-01-29 | Ｊｆｅスチール株式会社 | Steel sheet for container |
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| JP2002355921A (en) * | 2001-05-31 | 2002-12-10 | Nippon Steel Corp | Steel panel for container excellent in adhesion and corrosion resistance |
| JP2006009046A (en) * | 2004-06-22 | 2006-01-12 | Toyo Seikan Kaisha Ltd | Surface treated metallic material and its surface treatment method, resin-coated metallic material, metallic can and metallic lid |
| JP2006348360A (en) * | 2005-06-17 | 2006-12-28 | Toyo Seikan Kaisha Ltd | Surface-treated metallic plate, method of surface treating thereof and resin-coated metallic plate, metal can and can lid |
| JP2008184630A (en) * | 2007-01-29 | 2008-08-14 | Jfe Steel Kk | Surface treated metallic plate and method of manufacturing the same, resin coated metallic plate, metallic can and can cap |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014088589A (en) * | 2012-10-29 | 2014-05-15 | Jfe Steel Corp | Steel sheet for vessel, treatment liquid used for production thereof, and production method of steel sheet for vessel |
| WO2015012176A1 (en) * | 2013-07-24 | 2015-01-29 | Ｊｆｅスチール株式会社 | Steel sheet for container |
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