JP2005220364A - Steel sheet for welded can, and its production method - Google Patents
Steel sheet for welded can, and its production method Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 98
- 238000003466 welding Methods 0.000 claims abstract description 52
- 230000007797 corrosion Effects 0.000 claims abstract description 36
- 238000005260 corrosion Methods 0.000 claims abstract description 36
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005096 rolling process Methods 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 230000003746 surface roughness Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 239000003973 paint Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000002344 surface layer Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- 238000005868 electrolysis reaction Methods 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- -1 fluorine ions Chemical class 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005464 sample preparation method Methods 0.000 description 3
- 229910020900 Sn-Fe Inorganic materials 0.000 description 2
- 229910019314 Sn—Fe Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910020938 Sn-Ni Inorganic materials 0.000 description 1
- 229910008937 Sn—Ni Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005493 welding type Methods 0.000 description 1
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
Abstract
Description
本発明は、製缶素材として、特に溶接性、塗料密着性、フィルム密着性、耐食性に優れた溶接缶用鋼板及びその製造方法に関するものである。 TECHNICAL FIELD The present invention relates to a steel plate for a welding can that is particularly excellent in weldability, paint adhesion, film adhesion, and corrosion resistance as a can-making material, and a method for producing the same.
従来、溶接缶は、ワイヤーシーム溶接法により製缶され、コーヒー等のレトルト飲料や食缶用途として実用に供されてきた。この種の溶接缶に使用される缶用鋼板は、特開昭６０−２０８４９４号公報（特許文献１）、特開昭６０−１３０９８号公報（特許文献２）等に記載の方法により作製する事ができ、主にＳｎをめっきした鋼板が使用されている。これらのめっき鋼板の缶内相当側に、塗装あるいはフィルムがラミネートされ、缶外面相当側に、塗装、印刷あるいは印刷が施されたフィルムがラミネートされた後に、１缶相当分の大きさに切出され、溶接工程、ネック−フランジ加工等の工程を経て、溶接缶が製造される。溶接缶用鋼板にＳｎが使用されている理由は、２つあり、１つは高速で溶接を可能にする優れた溶接性の確保と優れた耐食性の確保にある。 Conventionally, welded cans have been produced by wire seam welding and have been put to practical use as retort beverages such as coffee and food cans. The steel plate for cans used in this type of welding can is manufactured by the method described in JP-A-60-208494 (Patent Document 1), JP-A-60-13098 (Patent Document 2) and the like. Steel plates plated with Sn are mainly used. After coating or film is laminated on the side corresponding to the inside of these plated steel sheets, and the coated, printed or printed film is laminated on the side corresponding to the outer surface of the can, it is cut into a size corresponding to one can. And a welding can is manufactured through processes, such as a welding process and neck-flange processing. There are two reasons why Sn is used in the steel sheet for welding cans. One is to ensure excellent weldability and excellent corrosion resistance that enable welding at high speed.
ワイヤーシーム溶接では、通常、交流電流が使用され、その半波で溶接ナゲットを形成させる。この溶接ナゲットの間隔は、使用する交流の周波数と溶接速度（ワイヤー速度）に依存し、一般的には、０．８〜１ｍｍ程度に設定されている。また、使用される電流は、低過ぎると十分な溶接強度が得られず、高過ぎると過熱（オーバーヒート）による散りが発生し、内容物への鉄溶出が懸念される事から、適度な電流値を設定する必要がある。 In wire seam welding, an alternating current is usually used, and a welding nugget is formed by the half wave. The interval between the weld nuggets depends on the AC frequency used and the welding speed (wire speed), and is generally set to about 0.8 to 1 mm. In addition, if the current used is too low, sufficient welding strength cannot be obtained. If it is too high, scattering due to overheating (overheating) occurs, and there is a concern about iron elution into the contents. Need to be set.
近年、溶接品位を向上させるため、ナゲット間隔を０．５ｍｍ以下に狭くする溶接方法が行われる様になってきた。ナゲット間隔が狭くなると、過熱による散りの発生を抑制することが出来、更に、設定電流の調整巾を広げる事が出来る。
しかし、ナゲット間隔が狭くなると、溶接電流が高くなるため、電極と鋼板間の発熱量が増加し、めっきされたＳｎが飛散する現象が顕著になってきた。飛散したＳｎは溶接ヘッド近傍のＺバーやツールに付着、堆積し、ある大きさになると溶接部に落下し、溶接不良の原因になることから、この現象の抑制が求められるようになった。
In recent years, in order to improve the welding quality, a welding method for narrowing the nugget interval to 0.5 mm or less has been performed. When the nugget interval is narrowed, the occurrence of scattering due to overheating can be suppressed, and further, the adjustment range of the set current can be expanded.
However, when the nugget interval is narrowed, the welding current increases, so the amount of heat generated between the electrode and the steel sheet increases, and the phenomenon that the plated Sn scatters becomes prominent. The scattered Sn adheres to and accumulates on the Z bar and tool near the welding head, drops to a welded portion when it reaches a certain size, and causes defective welding. Therefore, suppression of this phenomenon has been demanded.
発明者らは、上記のＳｎが飛散する現象を鋭意調査し、その解決策を検討した結果、以下の結論を得た。即ち、溶接時のＳｎ飛散量は溶接電流に依存するが、鋼板表面の凹凸にも依存し、鋼板表面の凸部は、溶接電流が集中し易く、その結果、局部発熱が生じ、Ｓｎの飛散を増幅していることが明らかになった。そこで、鋼板表面の凸部を極力少なくした鋼板を作製し、該現象の抑制を検討した処、使用する溶接電流が著しく増加し、それに伴いＳｎ飛散量も増加すると言う逆の結果が得られる事が明らかになった。これは、鋼板表面の凸部が無くなった事により、鋼板同士の表面での接触が、鋼板表面の凸部を中心にした接触から、凸部のない平らな面を中心にした表面に変化した為、接触抵抗が低下した事が原因であると考えられる。 The inventors diligently investigated the phenomenon of the above Sn scattering, and as a result of studying the solution, the following conclusions were obtained. That is, the amount of Sn scattering during welding depends on the welding current, but also depends on the unevenness on the surface of the steel sheet. The convexity on the surface of the steel sheet tends to concentrate the welding current, resulting in local heat generation and Sn scattering. It became clear that it was amplifying. Therefore, a steel sheet with as few protrusions as possible on the surface of the steel sheet was prepared, and the suppression of this phenomenon was studied. As a result, the welding current used increased remarkably, and the consequent result was that the amount of Sn scattering increased. Became clear. This is because the protrusions on the steel sheet surface disappeared, and the contact between the surfaces of the steel sheets changed from the contact centered on the protrusions on the steel sheet surface to the surface centered on the flat surface without the protrusions. Therefore, it is considered that the contact resistance is lowered.
発明者らは、これらの現象を詳細に解析すると共に、種々の表面凹凸を有する鋼板を作製し、Ｓｎ飛散状況を検討した結果、微細かつ高さに大きなばらつきのない凸部を多数有する表面を有する鋼板が、溶接電流を上げる事無く、しかも、溶接時のＳｎの飛散量を減少せしめる効果を有し、更に、これらの現象がめっき鋼板の粗度を表す指標である最大高さ（ＪＩＳ Ｂ ０６０１ 参照、以下、Ｒｍａｘと呼ぶ）、中心線平均粗さ（算術平均高さ、ＪＩＳ Ｂ ０６０１参照、以下、Ｒａと呼ぶ）、高さ０．２５μｍ以上のピーク数（以下、Ｐｃ、ピークカウントと呼ぶ）で極めて高い相関がある事を見出すに至ったものである。 The inventors analyzed these phenomena in detail and produced steel sheets having various surface irregularities and studied the Sn scattering state. As a result, the inventors found a surface having a large number of projections that are fine and have no great variation in height. The steel plate has the effect of reducing the amount of Sn scattering during welding without increasing the welding current, and further, these phenomena are the maximum height (JIS B) which is an index representing the roughness of the plated steel plate. 0601, hereinafter referred to as Rmax), center line average roughness (arithmetic average height, see JIS B 0601, hereinafter referred to as Ra), height of 0.25 μm or more peaks (hereinafter referred to as Pc, peak count) It has been found that there is a very high correlation.
本発明の要旨とするところは、
（１）鋼板に３００〜３０００ｍｇ／ｍ2 のＳｎめっきが施された後、溶融溶錫処理により、Ｓｎめっきの一部が合金化されると共に、凸部を有するＳｎめっき層が形成され、最表層に金属Ｃｒ換算量で、２〜３０ｍｇ／ｍ2 のクロメート皮膜が付与されためっき鋼板であって、めっき鋼板表面の、圧延方向に対して直角及び平行方向の粗度が、最大高さで５μｍ以下、中心線平均粗さで０．１〜０．４μｍ、高さ０．２５μｍ以上のピーク数で４０〜４００個／ｃｍである事を特徴とした溶接性、塗料密着性、フィルム密着性、耐食性に優れた溶接缶用鋼板。
The gist of the present invention is that
(1) After 300 to 3000 mg / m 2 of Sn plating is applied to the steel sheet, a part of the Sn plating is alloyed by a molten tin treatment, and a Sn plating layer having a convex portion is formed. It is a plated steel sheet to which a chromate film of 2 to 30 mg / m 2 is applied to the surface layer in terms of metallic Cr, and the roughness of the plated steel sheet surface in the direction perpendicular to and parallel to the rolling direction is the maximum height. Weldability, paint adhesion, and film adhesion characterized by 5 μm or less, center line average roughness of 0.1 to 0.4 μm, and height of 0.25 μm or more of 40 to 400 pieces / cm. Steel plate for welding can with excellent corrosion resistance.
（２）鋼板にＮｉを５〜１５０ｍｇ／ｍ2 含む、Ｎｉめっき層、Ｆｅ−Ｎｉ合金めっき層、Ｎｉ拡散層のうちの１種の下地層が施され、３００〜３０００ｍｇ／ｍ2 のＳｎめっきが施された後、溶融溶錫処理により、一部または全部の下地層がＳｎと合金化せしめられると共に、凸部を有するＳｎめっき層が形成され、最表層に金属Ｃｒ換算量で、２〜３０ｍｇ／ｍ2 のクロメート被膜が付与されためっき鋼板であって、めっき鋼板表面の、圧延方向に対して直角及び平行方向の粗度が、最大高さで５μｍ以下、中心線平均粗さで０．１〜０．４μｍ、高さ０．２５μｍ以上のピーク数で４０〜４００個／ｃｍである事を特徴とした溶接性、塗料密着性、フィルム密着性、耐食性に優れた溶接缶用鋼板。
（３）Ｓｎめっき層中に含まれる合金化していない金属Ｓｎ（フリーＳｎ）が１００ｍｇ／ｍ2 以上であることを特徴とする前記（１）または（２）記載の溶接性、塗料密着性、フィルム密着性、耐食性に優れた溶接缶用鋼板。
(2) The steel plate is coated with one of the base layers of Ni plating layer, Fe—Ni alloy plating layer, and Ni diffusion layer containing 5-150 mg / m 2 of Ni, and Sn plating of 300 to 3000 mg / m 2 Is applied, and a molten or tin-plated process causes a part or all of the underlayer to be alloyed with Sn, and a Sn plating layer having a convex portion is formed. A plated steel sheet to which a chromate film of 30 mg / m 2 is applied, and the roughness of the surface of the plated steel sheet perpendicular to and parallel to the rolling direction is 5 μm or less at the maximum height and 0 at the center line average roughness. A steel plate for a welding can excellent in weldability, paint adhesion, film adhesion, and corrosion resistance, characterized by having a peak number of from 1 to 0.4 μm and a height of 0.25 μm or more and 40 to 400 pieces / cm.
(3) Non-alloyed metal Sn (free Sn) contained in the Sn plating layer is 100 mg / m 2 or more, weldability, paint adhesion, (1) or (2), Steel sheet for welding cans with excellent film adhesion and corrosion resistance.
（４）圧延方向に対して直角及び平行方向の粗度が、最大高さで７μｍ以下、中心線平均粗さで０．１〜０．６μｍ、高さ０．２５μｍ以上のピーク数で５０〜５００個／ｃｍである粗度を有する調質圧延鋼板に３００〜３０００ｍｇ／ｍ2 のＳｎめっきを施した後、溶融溶錫処理により、Ｓｎめっきの一部を合金化せしめると共に、凸部を有するＳｎめっき層を形成させ、最表層に金属Ｃｒ換算量で、２〜３０ｍｇ／ｍ2 のクロメート皮膜を付与し、めっき鋼板表面の、圧延方向に対して直角及び平行方向の粗度を、最大高さで５μｍ以下、中心線平均粗さで０．１〜０．４μｍ、高さ０．２５μｍ以上のピーク数で４０〜４００個／ｃｍとすることを特徴とした溶接性、塗料密着性、フィルム密着性、耐食性に優れた溶接缶用鋼板の製造方法。 (4) The roughness in the direction perpendicular to and parallel to the rolling direction has a maximum height of 7 μm or less, a centerline average roughness of 0.1 to 0.6 μm, and a peak number of 50 to 0.25 μm in height. After applying 300 to 3000 mg / m 2 of Sn plating to a temper rolled steel sheet having a roughness of 500 pieces / cm, a part of the Sn plating is alloyed by molten tin treatment and has a convex portion. An Sn plating layer is formed, a 2 to 30 mg / m 2 chromate film is applied to the outermost layer in terms of metal Cr, and the roughness of the plated steel sheet surface in the direction perpendicular to and parallel to the rolling direction is maximized. 5 μm or less, center line average roughness of 0.1 to 0.4 μm, height of 0.25 μm or more of peak number of 40 to 400 / cm, weldability, paint adhesion, film A method for producing a steel sheet for a welding can excellent in adhesion and corrosion resistance.
（５）鋼板にＮｉを５〜１５０ｍｇ／ｍ2 含む、Ｎｉめっき層、Ｆｅ−Ｎｉ合金めっき層、Ｎｉ拡散層の１種の下地層を施し、３００〜３０００ｍｇ／ｍ2 のＳｎめっきを施した後、溶融溶錫処理により、一部または全部の下地層をＳｎと合金化せしめると共に、凸部を有するＳｎめっき層を形成させ、最表層に金属Ｃｒ換算量で、２〜３０ｍｇ／ｍ2 のクロメート皮膜を付与し、めっき鋼板表面の、圧延方向に対して直角及び平行方向の粗度を、最大高さで５μｍ以下、中心線平均粗さで０．１〜０．４μｍ、高さ０．２５μｍ以上のピーク数で４０〜４００個／ｃｍとすることを特徴とした溶接性、塗料密着性、フィルム密着性、耐食性に優れた溶接缶用鋼板の製造方法。
（６）Ｓｎめっき層中に含まれる合金化していない金属Ｓｎ（フリーＳｎ）を１００ｍｇ／ｍ2 以上とすることを特徴とする前記（４）または（５）記載の溶接缶用鋼板の製造方法にある。
(5) including 5 to 150 mg / m 2 of Ni in the steel sheet, Ni-plated layer, Fe-Ni alloy plating layer is subjected to one of the underlying layer of Ni diffusion layer was subjected to Sn plating 300~3000mg / m 2 Thereafter, a part or all of the underlayer is alloyed with Sn by molten tin treatment, and a Sn plating layer having a convex portion is formed, and the outermost layer is 2 to 30 mg / m 2 in terms of metal Cr. A chromate film is applied, and the surface roughness of the plated steel sheet in a direction perpendicular to and parallel to the rolling direction is 5 μm or less at the maximum height, 0.1 to 0.4 μm at the center line average roughness, and a height of 0.1 mm. The manufacturing method of the steel plate for welding cans excellent in weldability, coating-material adhesiveness, film adhesiveness, and corrosion resistance characterized by being 40-400 pieces / cm with the peak number of 25 micrometers or more.
(6) The method for producing a steel plate for a welding can according to (4) or (5), wherein the non-alloyed metal Sn (free Sn) contained in the Sn plating layer is 100 mg / m 2 or more. It is in.
表１に示すように、本特許により製造された溶接缶用鋼板は、優れた溶接性、塗料密着性、フィルム密着性、耐食性を有することが明らかになった。 As shown in Table 1, it became clear that the steel plate for welding cans manufactured according to this patent has excellent weldability, paint adhesion, film adhesion, and corrosion resistance.
以下、本発明について詳述する。
本発明で用いられる原板の表面粗度は、本発明の本質とする処であるめっき後の製品形態としての表面粗度に影響を与えることから以下のように規制される。
即ち、本発明のめっき後の最終製品としての表面粗度が、圧延方向に対して直角及び平行方向の粗度として、Ｒｍａｘで５μｍ以下、Ｒａで０．１〜０．４μｍ、Ｐｃで５０〜５００個／ｃｍを有する事を特徴としている。
Hereinafter, the present invention will be described in detail.
Since the surface roughness of the original plate used in the present invention affects the surface roughness as a product form after plating, which is the essence of the present invention, it is regulated as follows.
That is, the surface roughness as the final product after plating of the present invention is 5 μm or less in Rmax, 0.1 to 0.4 μm in Ra, and 50 to 50 in Pc as roughness in a direction perpendicular to and parallel to the rolling direction. It is characterized by having 500 pieces / cm.
この様な表面形態を有するめっき鋼板を製造するには、２つのポイントがあり、その１つはＳｎを凸状にめっきし表面に凹凸を形成させ、所在のＲａ、Ｐｃを確保する事と、もう１つは適度な表面粗度を有する原板（調質圧延）を使用することであり、どちらか一方が欠けても、本発明とする処の性能を有する溶接缶用鋼板を製造する事はできない。 To manufacture a plated steel sheet having such a surface form, there are two points, one of which is to form Sn on the surface by forming Sn in a convex shape, and to ensure Ra, Pc where it exists, The other is to use an original sheet (tempered rolling) having an appropriate surface roughness, and even if one of them is missing, it is possible to produce a steel sheet for a welding can having the performance of the present invention. Can not.
これは、Ｓｎめっき後に行われる溶融溶錫処理により凸上のＳｎを形成せしめると共に、溶融したＳｎの一部が原板の粗度の谷部に流れ込み、粗度が平滑化される。このため、原板には、溶融溶錫処理による粗度の平滑化を考慮し、粗めの粗度を用いる事が重要であるが、余り粗すぎると、凸状Ｓｎの形成が阻害されるため、適度な粗度が要求される。従って、本発明に用いられる原板の粗度は、Ｒｍａｘで７μｍ以下、Ｒａで０．５μｍ以下、及び、Ｐｃで５００以下にする必要がある。
一方、原板の粗度が低く、平滑になれば凸状のＳｎが形成し易くなるが、低くなり過ぎると、前述した、粗度の谷部へのＳｎ流れ込み現象により、所定のめっき鋼板の粗度が作製不能になる。従って、原板の粗度は、Ｒａで０．１μｍ以上、Ｐｃで５０以上にする必要がある。
This is because convex Sn is formed by the molten tin treatment performed after Sn plating, and a part of the molten Sn flows into the roughness valley of the original plate, and the roughness is smoothed. For this reason, it is important to use a rougher roughness for the original plate in consideration of the smoothness of the roughness due to the molten tin treatment, but if too rough, the formation of the convex Sn is hindered. A moderate roughness is required. Therefore, the roughness of the original plate used in the present invention must be 7 μm or less for Rmax, 0.5 μm or less for Ra, and 500 or less for Pc.
On the other hand, if the roughness of the original sheet is low and smooth, convex Sn can be easily formed. However, if the original sheet is too low, the roughness of a predetermined plated steel sheet is caused by the phenomenon of Sn flowing into the valley of the roughness described above. The degree becomes impossible to make. Therefore, the roughness of the original plate needs to be 0.1 μm or more for Ra and 50 or more for Pc.
この様なめっき原板を作製するためには、通常の原板を製造する工程において、熱間圧延、酸洗、冷間圧延、焼鈍後の調質圧延を行うことが望ましい。調質圧延工程では複数あるスタンドに設置されている圧延ロールに板を通板し、所定の材質と表面粗度が形成される。圧延ロールには、表面に多数の溝を入れたスクラッチロールや微細な凹凸を形成させたダルロールがあるが、ダルロールには表面にレーザーを照射し微細な穴を多数付与したレーザーダルロールを使用しても良い。 In order to produce such a plating original sheet, it is desirable to perform hot rolling, pickling, cold rolling, and temper rolling after annealing in the process of manufacturing a normal original sheet. In the temper rolling process, a plate is passed through rolling rolls installed on a plurality of stands, and a predetermined material and surface roughness are formed. There are scratch rolls with many grooves on the surface and dull rolls with fine irregularities formed on the rolls. For the dull rolls, laser dull rolls are used that are irradiated with a laser to give many fine holes. May be.
圧延方向に直角及び平行方向に所定の粗度を付与するには、方向性の少ないダルロールを使用することが望ましいが、スクラッチロールとダルロールを組み合わせても構わない。また、より精密に表面粗度を制御するには、めっきラインの酸洗工程で通常行われる陰極処理の代わりに陽極処理を行い、地鉄を部分的に溶解する事によって行う事もできる。 In order to give a predetermined roughness in a direction perpendicular to the rolling direction and in a parallel direction, it is desirable to use a dull roll with less directionality, but a scratch roll and a dull roll may be combined. Further, in order to control the surface roughness more precisely, it can be performed by anodizing instead of the cathodic treatment usually performed in the pickling process of the plating line, and partially dissolving the base iron.
上記によって作製された原板には、Ｎｉめっきが施されるのが望ましい。Ｎｉはそれ自体耐食性に優れた金属であると共にＳｎと合金化した合金層は非常に優れた耐食性を発揮する事から、内容物に対する耐食性を確保する為に用いられる。Ｎｉめっき量が５ｍｇ／ｍ2 を下回ると、実用的に優れた耐食性の向上効果が得られ難い為、Ｎｉめっき量は、５ｍｇ／ｍ2 以上が望ましい。Ｎｉめっき量が増加に伴い、その耐食性向上効果も増加するが、１５０ｍｇ／ｍ2 を超えると、その向上効果は飽和する事から、経済的観点からＮｉめっき量は１５０ｍｇ／ｍ2 以下で十分である。 The original plate produced as described above is preferably subjected to Ni plating. Ni is a metal excellent in corrosion resistance itself, and an alloy layer alloyed with Sn exhibits extremely excellent corrosion resistance, and is used to ensure corrosion resistance to the contents. When Ni plating amount is below 5 mg / m 2, practically excellent for hard improving effect is obtained for corrosion resistance, Ni plating amount, 5 mg / m 2 or more. As the Ni plating amount increases, the corrosion resistance improvement effect also increases. However, if the Ni plating amount exceeds 150 mg / m 2 , the improvement effect is saturated. Therefore, the Ni plating amount is not more than 150 mg / m 2 from an economical viewpoint. is there.
また、めっきされるＮｉは、Ｎｉ単体、Ｆｅ−Ｎｉ合金めっき、或いは、Ｎｉ拡散めっきの何れを用いても良い。また、これらのＮｉ系めっきのめっき方法としては、工業生産性等を考慮すると、３つの形態が考えられる。（１）通常の電気めっき法或いは置換めっき法などの電気化学的な方法によりＮｉ単体をめっきする方法、（２）電気化学的にＦｅ−Ｎｉ合金めっきを行う方法、（３）（１）によりＮｉめっきを行った後に、焼鈍等の工程を利用して加熱処理を行い、Ｎｉを拡散させる方法があり、何れの方法を用いても構わない。 The Ni to be plated may be any of Ni simple substance, Fe—Ni alloy plating, or Ni diffusion plating. In addition, as a plating method of these Ni-based plating, three forms are considered in consideration of industrial productivity and the like. (1) A method of plating Ni alone by an electrochemical method such as a normal electroplating method or a displacement plating method, (2) a method of electrochemically performing Fe-Ni alloy plating, (3) by (1) After performing Ni plating, there is a method of diffusing Ni by performing heat treatment using a process such as annealing, and any method may be used.
Ｎｉめっきに引続き、Ｓｎめっきが行われる。Ｓｎめっきの目的は、耐食性と溶接性の確保である。Ｓｎはそれ自体耐食性に優れているだけで無く、次に述べる溶融溶錫処理により、めっきしたＳｎの一部を下地と合金化させ、Ｓｎ−Ｆｅ合金、Ｓｎ−Ｎｉ合金、或いは、Ｓｎ−Ｆｅ−Ｎｉ合金を形成し、これらの合金が優れた耐食性を発揮する。また、Ｓｎはワイヤーシーム溶接において、電気抵抗を下げ、安定した溶接を可能にせしめる効果を有しており、Ｓｎめっきが施された鋼板の溶接性は飛躍的に向上する。このＳｎの優れた耐食性と溶接性が実用的に優れた効果を発揮するには、Ｓｎめっき量として３００ｍｇ／ｍ2 以上が必要である。３００ｍｇ／ｍ2 以下では実用上不十分な効果しか得られない。 Subsequent to the Ni plating, Sn plating is performed. The purpose of Sn plating is to ensure corrosion resistance and weldability. Sn is not only excellent in corrosion resistance, but also a part of the plated Sn is alloyed with the base by the molten tin treatment described below, and Sn—Fe alloy, Sn—Ni alloy, or Sn—Fe. -Ni alloys are formed, and these alloys exhibit excellent corrosion resistance. In addition, Sn has the effect of lowering electrical resistance and enabling stable welding in wire seam welding, and the weldability of a steel plate on which Sn plating has been applied is dramatically improved. In order for the excellent corrosion resistance and weldability of Sn to exhibit practically excellent effects, an Sn plating amount of 300 mg / m 2 or more is required. If it is 300 mg / m 2 or less, only a practically insufficient effect can be obtained.
Ｓｎめっきが多くなる程、耐食性、溶接性は向上するが、Ｓｎめっき量が３０００ｍｇ／ｍ2 を超えると耐食性、溶接性の向上効果は飽和してくるので、経済的な観点からＳｎめっき量は３０００ｍｇ／ｍ2 以下にすれば良い。更に、このＳｎの優れた溶接性は合金化していないＳｎ（以下フリーＳｎと呼ぶ）において著しい効果を有し、より高速で安定した溶接を行うには、少なくとも１００ｍｇ／ｍ2 以上のフリーＳｎを確保することが望ましい。Ｓｎめっきの方法については、特に規制しない。公知の電気めっき法や溶融したＳｎに浸漬してめっきする方法を用いれば良い。 As the Sn plating increases, the corrosion resistance and weldability improve. However, if the Sn plating amount exceeds 3000 mg / m 2 , the effect of improving the corrosion resistance and weldability is saturated. It may be 3000 mg / m 2 or less. Furthermore, the excellent weldability of Sn has a significant effect on non-alloyed Sn (hereinafter referred to as free Sn), and in order to perform welding at higher speed and more stably, free Sn of at least 100 mg / m 2 or more is required. It is desirable to ensure. There is no particular restriction on the Sn plating method. A known electroplating method or a method of plating by immersing in molten Sn may be used.
Ｓｎめっきに引続き、Ｓｎ合金層の形成と多数の凸状Ｓｎを均一に形成させる為に、溶融溶錫処理が施される。溶融溶錫処理とは、Ｓｎを短時間（数十秒以内）でＳｎ融点を超える２４０℃程度迄、加熱した後、８０℃から９０℃の温水に浸漬し、冷却する処理のことである。この処理により、溶融したＳｎが凝集し、多数の凸状Ｓｎを形成すると共に、一部のＳｎは流動し、原板粗度の窪みに流れ込み、凸状Ｓｎと原板の粗度の凹凸の相互作用により新たな表面形態を有するめっき鋼板が形成される。 Subsequent to the Sn plating, a molten tin treatment is performed in order to form the Sn alloy layer and to form a large number of convex Sns uniformly. The molten tin treatment is a treatment in which Sn is heated to about 240 ° C. exceeding the Sn melting point in a short time (within several tens of seconds), then immersed in warm water of 80 ° C. to 90 ° C. and cooled. By this treatment, melted Sn aggregates to form a large number of convex Sns, and part of Sn flows and flows into the depressions of the roughness of the original plate, and the interaction between the convex Sn and the roughness irregularities of the original plate. Thus, a plated steel sheet having a new surface form is formed.
この新たに形成された表面の粗度の形状が、本発明の本質とする処の効果を発揮する。即ち、先述の溶接時におけるＳｎの飛散現象は、鋼板凸部における局部発熱による事から、めっき鋼板の粗度が粗くなる程、即ち、Ｒｍａｘ、Ｒａ、Ｐｃが大きくなる程、Ｓｎの飛散現象は顕在化する。その為、めっき鋼板の粗度は、Ｒｍａｘで０．５μｍ以下、Ｒａで０．４μｍ以下、Ｐｃで５００以下にする必要がある。めっき鋼板がこれらの数値を超えると、溶接ヘッド近傍のＺバーやツールに付着、堆積したＳｎを除去する為、溶接機を一時停止しなければならない。その為、生産性が著しく阻害されることから、めっき鋼板の粗度は、所定の数値に規制する必要がある。 This newly formed roughness shape of the surface exhibits the effect which is the essence of the present invention. That is, the phenomenon of Sn scattering during welding described above is due to local heat generation at the convex portion of the steel sheet. Therefore, as the roughness of the plated steel sheet increases, that is, as Rmax, Ra, and Pc increase, the phenomenon of Sn scattering increases. Realize. Therefore, the roughness of the plated steel sheet needs to be 0.5 μm or less in Rmax, 0.4 μm or less in Ra, and 500 or less in Pc. If the plated steel sheet exceeds these values, the welder must be temporarily stopped to remove Sn deposited and deposited on the Z bar and tool near the welding head. Therefore, the productivity is remarkably hindered, so the roughness of the plated steel sheet needs to be regulated to a predetermined numerical value.
一方、めっき鋼板の粗度が平滑になる程、即ち、Ｒｍａｘ、Ｒａ、Ｐｃが小さくなる程、Ｓｎの飛散量は減少する。しかし、過度に粗度が平滑になると、板−板間の接触抵抗が著しく低下し、溶接電流を高くしなければ溶接が出来なくなる。先述した如く、溶接電流が高い程、発熱が多くなる為、Ｓｎの飛散は激しくなる事が判っている。従って、めっき鋼板の粗度は、Ｒａで０．１以上、Ｐｃで５０以上を確保する必要がある。この規定値を確保すれば、接触抵抗の低下を防止し、溶接電流は上がる事無く、Ｓｎの飛散も抑制することができる。 On the other hand, the amount of Sn scattering decreases as the roughness of the plated steel plate becomes smoother, that is, as Rmax, Ra, and Pc become smaller. However, when the roughness becomes excessively smooth, the contact resistance between the plates is remarkably lowered, and welding cannot be performed unless the welding current is increased. As described above, it is known that the higher the welding current is, the more heat is generated, and the more the Sn is scattered. Therefore, it is necessary to ensure the roughness of the plated steel sheet at 0.1 or more for Ra and 50 or more for Pc. If this specified value is secured, the contact resistance can be prevented from decreasing, the welding current does not increase, and the scattering of Sn can also be suppressed.
以上述べた性能を有する凸状Ｓｎを溶融溶錫処理の際に製造する方法については、特に規制しない。加熱についても公知の通電加熱や誘導加熱を用いれば良い。しかし、工業的に安定した本発明鋼板の本質とする処の表面粗度を得るには、例えば、Ｓｎめっき後に、フラックスを凸状Ｓｎの大きさ程度に点状に分散塗布させ、溶融時にＳｎが凝集し易くし、凸状Ｓｎを生成する方法や、加熱の際にレーザーを点状に照射し、凸状Ｓｎを形成させても良い。 The method for producing the convex Sn having the above-described performance during the molten tin treatment is not particularly restricted. As for the heating, known energization heating or induction heating may be used. However, in order to obtain the surface roughness that is the essence of the steel sheet of the present invention that is industrially stable, for example, after Sn plating, the flux is dispersed and applied in the form of dots in the size of convex Sn, and Sn is melted Can be easily aggregated, and a method of generating convex Sn, or a laser irradiation in the form of dots during heating may be used to form convex Sn.
溶融溶錫処理の後、フィルム密着性、耐食性、（塗膜下腐食の防止）の確保を目的としてクロメート皮膜が付与される。ここで言うクロメート皮膜とは、水和酸化Ｃｒ単一の皮膜、即ち本来のクロメート皮膜といま一つは下層に金属Ｃｒ層、上層に水和酸化Ｃｒ層の二層よりなる皮膜の二つの場合を指している。水和酸化Ｃｒ層には、後述するめっき助剤である硫酸イオンやフッ素イオンなどを含む場合がある。フィルム密着性や耐食性は、この水和酸化Ｃｒの水酸基とラミネートされるフィルムの水酸基等の官能基が強固な化学的な結合を行うことによって確保される。 After the molten tin treatment, a chromate film is applied for the purpose of ensuring film adhesion, corrosion resistance, and (preventing corrosion under the coating film). The chromate film referred to here is a single film of hydrated Cr oxide, ie, the original chromate film and another film composed of two layers, a metal Cr layer in the lower layer and a hydrated Cr oxide layer in the upper layer. Pointing. The hydrated Cr oxide layer may contain sulfate ions or fluorine ions, which are plating aids described later. Film adhesion and corrosion resistance are ensured by a strong chemical bond between the hydroxyl group of the hydrated Cr oxide and the functional group such as the hydroxyl group of the laminated film.
しかし、水和酸化Ｃｒ皮膜は電気的に絶縁体のため電気抵抗が非常に高く、金属Ｃｒも融点が鉄より高く、両者とも溶接性を劣化せしめるマイナス要因である。そのため、良好なフィルム密着性、耐食性と実用的に溶接性を劣化せしめない適正なクロメート皮膜付着量が非常に重要となる。従って、クロメート皮膜付着量は金属Ｃｒ換算で片面当たり２〜３０ｍｇ／ｍ2 が極めて望ましい。 However, since the hydrated Cr oxide film is an electrical insulator, the electrical resistance is very high, and the Cr metal has a higher melting point than iron, both of which are negative factors that degrade the weldability. Therefore, it is very important to have good film adhesion, corrosion resistance, and an appropriate amount of chromate film that does not practically degrade weldability. Therefore, the amount of chromate film adhesion is extremely desirably 2 to 30 mg / m 2 per side in terms of metallic Cr.
即ち、クロメート皮膜付着量が２ｍｇ／ｍ2 未満では、フィルム密着性の向上、塗膜下腐食の防止に効果が得られないので、２ｍｇ／ｍ2 以上の付着量が望ましい。一方、クロメート皮膜付着量が３０ｍｇ／ｍ2 を越えると接触抵抗が著しく増加し、局部的な発熱による散りが発生し易くなり溶接性が劣化する。そのためクロメート皮膜付着量は３０ｍｇ／ｍ2 以下に規制される。 That is, if the chromate film adhesion amount is less than 2 mg / m 2 , the effect of improving the film adhesion and preventing the corrosion under the coating film cannot be obtained. Therefore, the adhesion amount of 2 mg / m 2 or more is desirable. On the other hand, if the amount of chromate film deposited exceeds 30 mg / m 2 , the contact resistance is remarkably increased, and scattering due to local heat generation is likely to occur, resulting in poor weldability. Therefore, the chromate film adhesion amount is regulated to 30 mg / m 2 or less.
クロメート処理方法は、各種のＣｒ酸のナトリウム塩、カリウム塩、アンモニウム塩の水溶液による浸漬処理、スプレー処理、電解処理などいずれの方法で行っても良いが、特に陰極電解処理が優れている。とりわけ、Ｃｒ酸にめっき助剤として硫酸イオン、フッ化物イオン（醋イオンを含む）あるいはそれらの混合物を添加した水溶液中での陰極電解処理が最も優れている。
尚、本発明における粗度の測定方法については、特に規制しない。ＪＩＳＢ６０１、ＪＩＳ Ｂ ６３３、ＪＩＳ Ｂ ６５１に基づき、市販の触針式或いは光学式の粗度測定器を用いて測定すれば良い。
The chromate treatment method may be any method such as immersion treatment with various sodium salts, potassium salts, and ammonium salts of Cr acid, spray treatment, electrolytic treatment, etc., but cathode electrolytic treatment is particularly excellent. In particular, cathodic electrolysis in an aqueous solution in which sulfate ions, fluoride ions (including soot ions) or a mixture thereof is added as a plating aid to Cr acid is most excellent.
In addition, the roughness measuring method in the present invention is not particularly restricted. Based on JIS B601, JIS B 633, and JIS B 651, measurement may be performed using a commercially available stylus type or optical roughness measuring instrument.
以下に本発明の実施例及び比較例について述べ、その結果を表１に示す。
（試料作製方法１）
通常の低炭素鋼板を冷間圧延後、焼鈍し、ダルロールを使って調質圧延を行い、０．１９ｍｍ厚のめっき原板を製造した。引続き、このめっき原板に、（１）に示す条件でＦｅ−Ｎｉ合金めっきを行った後、（２）に示す条件でＳｎめっきを行い、フラックスを点状に塗布し、通電加熱により溶融溶錫処理を行った。その後、（３）に示す条件でクロメート皮膜を生成させ試料を作製した。
Examples of the present invention and comparative examples are described below, and the results are shown in Table 1.
(Sample preparation method 1)
A normal low carbon steel sheet was cold-rolled and then annealed and tempered using a dull roll to produce a 0.19 mm thick plated original sheet. Subsequently, after this Fe-Ni alloy plating was performed on the original plating plate under the conditions shown in (1), Sn plating was performed under the conditions shown in (2), the flux was applied in the form of dots, and the molten molten tin was heated by electric heating. Processed. Thereafter, a chromate film was produced under the conditions shown in (3) to prepare a sample.
（１）Ｆｅ−Ｎｉ合金めっき条件
Ｎｉイオン：２５ｇ／ｌ、Ｆｅイオン：５０ｇ／ｌ、硫酸イオン：１５ｇ／ｌ、塩素イオン：１０ｇ／ｌ、ホウ酸：２０ｇ／ｌのめっき浴を用い、３５℃、１０Ａ／ｄｍ2 で電解した。電解時間は、めっき量等に応じて適当に調整した。
（２）Ｓｎめっき条件
Ｓｎイオン：１５ｇ／ｌ、フェノールスルホン酸イオン：１５ｇ／ｌ、光沢添加剤：１．２ｇ／ｌのめっき浴を用い、４０℃、８Ａ／ｄｍ2 で電解した。電解時間は、めっき量に応じて調整した。
（３）クロメート処理条件
酸化Ｃｒ：１００ｇ／ｌ、硫酸イオン：０．６ｇ／ｌのめっき浴を用い、４５℃、３０Ａ／ｄｍ2 で電解した。電解時間は、めっき量等に応じて適当に調整した。
(1) Fe—Ni alloy plating conditions 35 using a plating bath of Ni ion: 25 g / l, Fe ion: 50 g / l, sulfate ion: 15 g / l, chlorine ion: 10 g / l, boric acid: 20 g / l Electrolysis was performed at 10 ° C / dm 2 at 10 ° C. The electrolysis time was appropriately adjusted according to the plating amount and the like.
(2) Sn plating conditions Electrolysis was performed at 40 ° C. and 8 A / dm 2 using a plating bath of Sn ion: 15 g / l, phenolsulfonic acid ion: 15 g / l, and gloss additive: 1.2 g / l. The electrolysis time was adjusted according to the amount of plating.
(3) Chromate treatment conditions Electrolysis was performed at 45 ° C. and 30 A / dm 2 using a plating bath of Cr oxide: 100 g / l and sulfate ion: 0.6 g / l. The electrolysis time was appropriately adjusted according to the plating amount and the like.
（試料作製方法２）
通常の低炭素鋼板を冷間圧延後、焼鈍し、ダルロールとスクラッチロールを使って調質圧延を行い、０．１６ｍｍ厚のめっき原板を製造した。引続き、このめっき原板に、（１）に示す条件でＮｉめっきを行った後、（２）に示す条件でＳｎめっきを行い、誘導加熱に加えレーザー光を点状に照射し、溶融溶錫処理を行った。その後、（３）に示す条件でクロメート皮膜を生成させ試料を作製した。
(Sample preparation method 2)
A normal low carbon steel sheet was cold-rolled and then annealed, and tempered using a dull roll and a scratch roll to produce a 0.16 mm thick plated original sheet. Subsequently, Ni plating was performed on the original plate under the conditions shown in (1), then Sn plating was performed under the conditions shown in (2), and in addition to induction heating, a laser beam was irradiated in the form of dots, and molten tin treatment was performed. Went. Thereafter, a chromate film was produced under the conditions shown in (3) to prepare a sample.
（１）Ｎｉめっき条件
Ｎｉイオン：４０ｇ／ｌ、硫酸イオン：３５ｇ／ｌ、塩素イオン：１０ｇ／ｌ、ホウ酸：２０ｇ／ｌのめっき浴を用い、４０℃、５Ａ／ｄｍ2 で電解した。電解時間は、めっき量等に応じて適当に調整した。
（２）Ｓｎめっき条件
Ｓｎイオン：１５ｇ／ｌ、フェノールスルホン酸イオン：１５ｇ／ｌ、光沢添加剤：１．２ｇ／ｌのめっき浴を用い、４５℃、１２Ａ／ｄｍ2 で電解した。電解時間は、めっき量に応じて調整した。
（３）クロメート処理条件
Ｃｒ酸：８０ｇ／ｌ、硫酸イオン：０．０５ｇ／ｌ、ケイフッ化ソーダ：２．５ｇ／ｌ、フッ化アンモン：０．５ｇ／ｌのめっき浴を用い、３５℃、２５Ａ／ｄｍ2 で電解した。電解時間は、めっき量に応じて調整した。
(1) Ni plating conditions Electrolysis was performed at 40 ° C. and 5 A / dm 2 using a plating bath of Ni ions: 40 g / l, sulfate ions: 35 g / l, chlorine ions: 10 g / l, boric acid: 20 g / l. The electrolysis time was appropriately adjusted according to the plating amount and the like.
(2) Sn plating conditions Electrolysis was performed at 45 ° C. and 12 A / dm 2 using a plating bath of Sn ion: 15 g / l, phenolsulfonic acid ion: 15 g / l, and gloss additive: 1.2 g / l. The electrolysis time was adjusted according to the amount of plating.
(3) Chromate treatment conditions Cr acid: 80 g / l, sulfate ion: 0.05 g / l, sodium fluorosilicate: 2.5 g / l, ammonium fluoride: 0.5 g / l, 35 ° C. electrolysis was 25A / dm 2. The electrolysis time was adjusted according to the amount of plating.
（試料作製方法３）
通常の低炭素鋼板を冷間圧延後、（１）に示す条件でＮｉめっきを行った後、焼鈍し、ダルロールとスクラッチロールを使って調質圧延を行い、０．１７ｍｍ厚のめっき原板を製造した。引続き、このめっき原板に、（２）に示す条件でＳｎめっきを行い、誘導加熱に加えレーザー光を点状に照射し、溶融溶錫処理を行った。その後、（３）に示す条件でクロメート皮膜を生成させ試料を作製した。
(Sample preparation method 3)
After cold rolling a normal low carbon steel plate, after performing Ni plating under the conditions shown in (1), annealing and temper rolling using a dull roll and scratch roll to produce a 0.17 mm thick plating original plate did. Subsequently, Sn plating was performed on the original plating plate under the conditions shown in (2), and in addition to induction heating, a laser beam was irradiated in a dot shape to perform a molten tin treatment. Thereafter, a chromate film was produced under the conditions shown in (3) to prepare a sample.
（１）Ｎｉめっき条件
Ｎｉイオン：４０ｇ／ｌ、硫酸イオン：３５ｇ／ｌ、塩素イオン：１０ｇ／ｌ、ホウ酸：２０ｇ／ｌのめっき浴を用い、４０℃、５Ａ／ｄｍ2 で電解した。電解時間は、めっき量等に応じて適当に調整した。
（２）Ｓｎめっき条件
Ｓｎイオン：１５ｇ／ｌ、フェノールスルホン酸イオン：１５ｇ／ｌ、光沢添加剤：１．２ｇ／ｌのめっき浴を用い、４５℃、１２Ａ／ｄｍ2 で電解した。電解時間は、めっき量に応じて調整した。
（３）クロメート処理条件
酸化Ｃｒ：１００ｇ／ｌ、硫酸イオン：０．６ｇ／ｌのめっき浴を用い、４５℃、３０Ａ／ｄｍ2 で電解した。電解時間は、めっき量等に応じて適当に調整した。
(1) Ni plating conditions Electrolysis was performed at 40 ° C. and 5 A / dm 2 using a plating bath of Ni ions: 40 g / l, sulfate ions: 35 g / l, chlorine ions: 10 g / l, boric acid: 20 g / l. The electrolysis time was appropriately adjusted according to the plating amount and the like.
(2) Sn plating conditions Electrolysis was performed at 45 ° C. and 12 A / dm 2 using a plating bath of Sn ion: 15 g / l, phenolsulfonic acid ion: 15 g / l, and gloss additive: 1.2 g / l. The electrolysis time was adjusted according to the amount of plating.
(3) Chromate treatment conditions Electrolysis was performed at 45 ° C. and 30 A / dm 2 using a plating bath of Cr oxide: 100 g / l and sulfate ion: 0.6 g / l. The electrolysis time was appropriately adjusted according to the plating amount and the like.
〔試料評価方法〕
上記処理材について、以下に示す（Ａ）〜（Ｅ）の各項目について実施し、４段階（◎ ：非常に良好、○：良好、△：やや不良、×：極めて不良）で、その性能を評価した。（Ａ）溶接性
試料に溶接箇所を除いて厚さ１５μｍのＰＥＴフィルムをラミネートし、スードロニック社製溶接機にて、ラップ代：０．５ｍｍ、加圧力：４５ｋｇｆ、溶接速度：８０ｍ／ｍｉｎ、溶接電流：微小な散りが発生し始める電流値で３０分間溶接しＳｎの溶接ヘッド付近のＳｎ飛散及び付着状況を観察し、溶接性を評価した。
[Sample evaluation method]
About the said processing material, it implemented about each item of (A)-(E) shown below, and the performance was carried out in four steps (◎: Very good, ○: Good, Δ: Somewhat bad, X: Very bad). evaluated. (A) Weldability A PET film having a thickness of 15 μm is laminated on a sample except for a welding portion, and a lap allowance: 0.5 mm, a pressurizing force: 45 kgf, a welding speed: 80 m / min, welding with a welder manufactured by Sudronic. Current: Welding was performed for 30 minutes at a current value at which minute scattering began to occur, and Sn scattering and adhesion in the vicinity of the Sn welding head were observed to evaluate weldability.
（Ｂ）塗料密着性
試料にエポキシフェノール系塗料を５５ｍｇ／ｄｍ2 塗布し、更に缶外面に相当する面にクリヤーラッカーを４０ｍｇ／ｄｍ2 塗布し、２９０℃まで１５ｓｅｃの焼き付け条件で乾燥硬化した。引続き、各々の面に１ｍｍ間隔でスクラッチを入れ、約１００個の碁盤目を作製し、速やかにテープ剥離し、その剥離状況を観察し塗料密着性を評価した。
(B) Paint adhesion The sample was coated with 55 mg / dm 2 of epoxyphenol-based paint, and 40 mg / dm 2 of clear lacquer was applied to the surface corresponding to the outer surface of the can, and dried and cured to 290 ° C. under baking conditions of 15 sec. Subsequently, scratches were placed on each surface at intervals of 1 mm to produce about 100 grids, and the tape was peeled off quickly. The peeled state was observed to evaluate the paint adhesion.
（Ｃ）フィルム密着性評価試験
試料に厚さ１５μｍのＰＥＴフィルムをラミネートした後、地鉄に達するまでクロスカットを入れ、速やかに２４０℃に加熱し、クロスカット中央部に５ｋｇ／ｃｍ2 の空気ガスを垂直に吹きつけ、フィルムの剥離状況を評価した。
(C) After laminating a PET film having a thickness of 15 μm on a film adhesion evaluation test sample, a crosscut was made until it reached the ground iron, and it was quickly heated to 240 ° C., and 5 kg / cm 2 of air was placed in the center of the crosscut Gas was blown vertically to evaluate the film peeling state.
（Ｄ）塗膜下腐食性評価試験
試料に厚さ１５μｍＰＥＴフィルムをラミネートした。その後、地鉄に達するまでクロスカットを入れ、１．５％クエン酸−１．５％食塩混合液からなる試験液中に大気開放下５５℃×４日間浸漬した。試験終了後、速やかにスクラッチ部および平面部をテープで剥離して、スクラッチ部近傍の腐食状況、スクラッチ部のピッティング状況および平面部のフィルム剥離状況を判断して総合的に評価した。
(D) Undercoat corrosion resistance evaluation test A 15 μm thick PET film was laminated on the sample. Then, the crosscut was put in until it reached the ground iron, and it was immersed in the test liquid which consists of a 1.5% citric acid-1.5% sodium chloride mixed solution at 55 degreeC x 4 days in open air. Immediately after the test, the scratch part and the flat part were peeled off with tape, and the corrosion situation near the scratch part, the pitting situation of the scratch part and the film peeling situation of the flat part were judged and evaluated comprehensively.
（Ｅ）耐食性試験
試料に厚さ１５μｍのＰＥＴフィルムをラミネートした溶接缶を作製し、１．５％クエン酸−１．５％食塩混合液からなる試験液中を充填し、３８℃で６ヶ月間貯蔵し、腐食状況を観察し、耐食性を評価した。
(E) Corrosion resistance test A weld can obtained by laminating a 15 μm-thick PET film on a sample, filled in a test solution consisting of a 1.5% citric acid-1.5% salt mixture, and at 6 ° C. for 6 months It was stored for a while and the corrosion status was observed to evaluate the corrosion resistance.
代理人 弁理士 椎 名 彊 他１
Attorney Attorney Shiina and others 1
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011084820A (en) * | 2011-01-31 | 2011-04-28 | Jfe Steel Corp | Surface-treated steel sheet and method of manufacturing the same |
| CN116685051A (en) * | 2023-07-03 | 2023-09-01 | 广州方邦电子股份有限公司 | Metal foil, carrier foil, metal-clad laminate, printed wiring board, and battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011084820A (en) * | 2011-01-31 | 2011-04-28 | Jfe Steel Corp | Surface-treated steel sheet and method of manufacturing the same |
| CN116685051A (en) * | 2023-07-03 | 2023-09-01 | 广州方邦电子股份有限公司 | Metal foil, carrier foil, metal-clad laminate, printed wiring board, and battery |
| CN116685051B (en) * | 2023-07-03 | 2024-02-06 | 广州方邦电子股份有限公司 | Metal foil, carrier foil, metal-clad laminate, printed wiring board, and battery |
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