WO2011055481A1 - Method for producing surface-treated steel sheet - Google Patents
Method for producing surface-treated steel sheet Download PDFInfo
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- WO2011055481A1 WO2011055481A1 PCT/JP2010/005800 JP2010005800W WO2011055481A1 WO 2011055481 A1 WO2011055481 A1 WO 2011055481A1 JP 2010005800 W JP2010005800 W JP 2010005800W WO 2011055481 A1 WO2011055481 A1 WO 2011055481A1
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- WIPO (PCT)
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- steel sheet
- tin
- sulfate plating
- tin sulfate
- treated steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Definitions
- the present invention relates to a method for producing a surface-treated steel sheet for a resin-coated steel sheet having excellent work adhesion.
- a can body is manufactured by winding a top plate on a can body in which a can body portion and a can bottom portion are integrally formed.
- excellent adhesion of the resin to the steel sheet is required so that the coating resin does not peel or break during or after the severe forming process.
- resin-coated chromate-treated steel sheets in which an organic resin is coated on a chromate-treated steel sheet such as tin-free steel (TFS) with a chromate film having excellent processing adhesion on the surface are used as materials for these cans. It was.
- the plated steel sheet used for beverage cans mainly has tinplate (tin-plated steel sheet) and TFS (electrolytic chromium-plated steel sheet), but the filling of highly corrosive contents can utilize the sacrificial anticorrosive action of tin.
- the tinplate has better corrosion resistance than TFS.
- Tinplate has a tin oxide film (inhibits adhesion to the organic resin film) and is difficult to coat above the melting point of tin (232 ° C) (tin melts and becomes fluid and adheres to heating equipment) Therefore, it is difficult to cover at the melting point of tin or higher, and the film adhesion after canning is inferior to TFS.
- Patent Document 1 discloses a tin plating of a no-reflow tin-plated steel sheet (tin-plated steel sheet not subjected to tin fusion treatment) or a reflow tin-plated steel sheet (tin-plated steel sheet subjected to tin fusion treatment).
- a resin-coated tin-plated steel sheet in which a silane coupling agent coating layer is provided on a layer and an organic resin film is further laminated is described.
- the treatment of the resin-coated tin-plated steel sheet of Patent Document 1 adds a new treatment, not only does the manufacturing cost of the tinplate increase, but it also uses stretch and ironing in combination after drawing.
- the resin may peel off at the upper part of the can body during the molding process, and there was a problem in the processing adhesion of the resin during can body processing.
- the present invention solves the above-described problems and provides a method for producing a surface-treated steel sheet for a resin-coated steel sheet having excellent work adhesion even during severe forming, and a resin-coated steel sheet obtained by coating a resin on the surface-treated steel sheet The purpose is to provide.
- the method for producing the surface-treated steel sheet of the present invention is as follows: Sn concentration in a tin sulfate plating bath containing sulfuric acid and tin sulfate is 30 to 120 g / L, The temperature of the tin sulfate plating bath is 20 to 60 ° C. The current density in the tin sulfate plating is 2 to 50 A / dm 2 , In this range, the tin area ratio on the steel sheet surface is 5 to 95%, The surface of the steel sheet is coated with metallic tin so that a part of the iron on the steel sheet surface is exposed. (2) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
- Sn concentration in the tin sulfate plating bath is 30-50 g / L, The temperature of the tin sulfate plating bath is 30-60 ° C., A current density in the tin sulfate plating is 2 A / dm 2 or less.
- Sn concentration in the tin sulfate plating bath is 30-50 g / L, The temperature of the tin sulfate plating bath is 40-60 ° C. The current density in the tin sulfate plating is 2 to 5 A / dm 2 .
- the method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
- Sn concentration in the tin sulfate plating bath is 50 to 70 g / L, The temperature of the tin sulfate plating bath is 20 to 60 ° C., The current density in the tin sulfate plating is 2 to 5 A / dm 2 .
- the method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
- Sn concentration in the tin sulfate plating bath is 50 to 70 g / L
- the temperature of the tin sulfate plating bath is 30-60 ° C.
- the current density in the tin sulfate plating is 2 to 7 A / dm 2 .
- the method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
- Sn concentration in the tin sulfate plating bath is 50 to 70 g / L
- the temperature of the tin sulfate plating bath is 50-60 ° C.
- the current density in the tin sulfate plating is 2 to 10 A / dm 2 .
- Sn concentration in the tin sulfate plating bath is 70 to 90 g / L, The temperature of the tin sulfate plating bath is 20 to 60 ° C., The current density in the tin sulfate plating is 2 to 7 A / dm 2 .
- Sn concentration in the tin sulfate plating bath is 70 to 90 g / L, The temperature of the tin sulfate plating bath is 30-60 ° C., The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
- the method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
- Sn concentration in the tin sulfate plating bath is 70 to 90 g / L
- the temperature of the tin sulfate plating bath is 50-60 ° C.
- the current density in the tin sulfate plating is 2 to 15 A / dm 2 .
- Sn concentration in the tin sulfate plating bath is 90 to 120 g / L
- the temperature of the tin sulfate plating bath is 20 to 60 ° C.
- the current density in the tin sulfate plating is 2 to 10 A / dm 2 .
- the method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
- Sn concentration in the tin sulfate plating bath is 90 to 120 g / L
- the temperature of the tin sulfate plating bath is 40-60 ° C.
- the current density in the tin sulfate plating is 2 to 15 A / dm 2 .
- the method for producing a resin-coated steel sheet according to the present invention is characterized in that a resin is coated on the surface-treated steel sheet produced by the production method described in any one of (1) to (11).
- the method for producing a resin-coated steel sheet according to the present invention is characterized in that, in (12), the resin coating is performed at a temperature equal to or higher than a melting point of tin.
- the resin-coated steel sheet having a resin layer laminated thereon exhibits a work adhesion superior to that of the prior art.
- the resin layer laminated thereon adheres to the iron surface with good adhesion, and at the same time, a conventional flat surface with an anchor effect due to unevenness As compared with the tin-plated steel sheet, the adhesion with the resin layer can be greatly improved.
- a surface-treated steel sheet in which a part of iron is exposed and coated with tin can be coated with resin at a temperature equal to or higher than the melting point of tin (232 ° C.), and the adhesion of the resin layer after canning is also TFS. Shows excellent adhesion. That is, since tin is present on the entire surface of conventional tin-plated steel sheet, when the resin coating is performed at a temperature higher than the melting point of tin, the molten tin at the time of the tin melting process has fluidity and the appearance becomes uneven.
- the manufacturing method of the surface-treated steel sheet of the present invention can use a tin sulfate plating bath, and this bath uses inexpensive sulfuric acid instead of PSA (phenol sulfonic acid) which is a conventional ferrostantin plating bath component.
- FIG. It is the photograph (SEM image) which observed the cross section of the surface treatment steel plate at 45 degrees, (a) is the cross-sectional observation photograph of Example 1 of this invention, (b) is the cross-sectional observation photograph of the comparative example 1.
- FIG. It is a top view which shows the shape of the test piece for S peel strength measurement. It is a top view which shows the state which made the cut into the coating resin film surface of the test piece for S peel strength measurement. It is a top view which shows the state which put the score in the test piece for S peel strength measurement. It is a fragmentary sectional view of the test piece for S peel strength measurement which put the score. It is a schematic perspective view which shows the state which puts the test piece for S peel strength measurement in a test piece holder, and performs strength measurement.
- the steel sheet used as the original sheet of the surface-treated steel sheet of the present invention is a sheet thickness of 0.15 to 0.3 mm after annealing a low carbon aluminum killed hot rolled sheet generally used for cans.
- a cold-rolled steel sheet, a cold-rolled steel sheet that has been further cold-rolled after annealing to increase its strength, and the like are used depending on the application.
- a cold-rolled steel sheet manufactured from non-aging ultra-low carbon steel added with niobium and titanium is also applicable. After these cold-rolled steel sheets are electrolytically degreased and pickled, a tin-plated layer is formed on the steel sheets to obtain surface-treated steel sheets.
- the surface-treated steel sheet uses a tin sulfate plating bath in the present invention.
- Tin sulfate concentration (as Sn concentration): 30 to 120 g / L
- surfactants and antioxidants can be added.
- Plating current density 2 to 50 A / dm 2
- Plating bath temperature 20 to 60 ° C.
- tin sulfate concentration Sn concentration
- the concentration is likely to fluctuate and accurate plating operation may be difficult.
- the pH becomes too low, and the corrosiveness of the plating solution becomes high, which may contaminate the plating solution.
- Plating current density 2 to 50 A / dm 2 is less than 2 A / dm 2 because it takes a long time to finish the plating process, and accurate plating operation is difficult due to variations in plating solution components There is.
- it exceeds 50 A / dm 2 the entire surface is plated and the underlying iron is not exposed.
- the reason for the plating bath temperature 20 to 60 ° C.
- the surface tin area ratio is 95% or more, and it is close to the entire surface coating (no underlying iron exposed), and the film non-adhesion is significantly reduced.
- the concentration of components in the plating solution tends to fluctuate, and accurate plating is difficult.
- the area occupied on the steel plate by the metal tin dispersed and deposited on the steel plate is preferably 5 to 95%. If the surface tin area ratio is less than 5%, the corrosion resistance and workability are remarkably deteriorated, so a tin area ratio of at least 5% is required. When the surface tin area ratio exceeds 95%, the exposed area of iron is reduced and does not contribute to the improvement of the adhesion of the resin layer. This is because at least 5% or more of the exposed area of iron is required to improve the adhesion with the resin layer.
- the surface tin area ratio on this steel sheet is the one observed by the electron microscope, the first image, and the tin dispersed and present on the steel sheet surface was chemically removed, and then observed again by the electron micrograph.
- the second image can be obtained by comparing both obtained images by computer image processing.
- the tin plating amount of metallic tin on the steel sheet surface is preferably in the range of 0.1 to 13 g / m 2 from the viewpoint of exposing the iron surface in an area of 5% or more. Preferably, it is 0.5 to 5.6 g / m 2 . If the tin plating amount is less than 0.1 g / m 2 , the corrosion resistance is insufficient, which is not preferable. In particular, when tin melting (reflow) treatment is performed, all of the plated tin becomes an Fe—Sn alloy, and not only the corrosion resistance but also the workability is remarkably deteriorated.
- a tin plating amount of at least 0.1 g / m 2 or more is required. I need. On the other hand, when it exceeds 13 g / m 2 , iron is not exposed to the surface, and does not contribute to the improvement of the adhesion of the resin layer.
- the average particle size of metal tin (the average particle size as seen from the plane) is desirably 0.5 to 50 ⁇ m.
- the thickness is 2 to 20 ⁇ m.
- the particle size is less than 0.5 ⁇ m, the particle size is too small, and the anchor effect of the resin layer due to the unevenness cannot be sufficiently obtained, which does not contribute to the improvement of the adhesion of the resin layer.
- the average particle size exceeds 50 ⁇ m, it is difficult to deposit tin due to restrictions on electrolytic treatment.
- the resin film used as a resin layer is laminated
- a thermoplastic resin excellent in processability after heating is preferable, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene terephthalate / ethylene isophthalate copolymer, butylene terephthalate / butylene isophthalate copolymer, etc.
- Polyester resin or a blend of two or more of these polyester resins, polyethylene, polypropylene, ethylene / propylene copolymer, and those modified with maleic acid, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer
- Polyolefin resins such as polymers, polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon, polycarbonate, polymethylpentene, and polyester resins described above Resin layer of a single layer consisting of a blend of ionomer, and a further resin layer of the multi-layer consisting of two or more kinds of these resins.
- the thickness of the resin layer includes the ease of resin layer laminating work, the adhesion strength of the resin layer to the surface-treated steel sheet in a molded body (such as a can) after the resin-coated steel sheet is formed, corrosion resistance, and economic efficiency. From the viewpoint, it is preferably 10 to 100 ⁇ m.
- These resin layers are heat-melted resin pellets, extruded from a T-die of an extruder to form a film with a desired thickness, and surface treatment on which metal tin with an exposed iron surface is formed It is formed by laminating on a steel plate.
- a method for laminating the resin layer for example, a thermal bonding method is used.
- the resin film is brought into contact with a surface-treated steel sheet heated to a predetermined temperature range, and sandwiched from both sides with a pair of pressure rolls. Press to join.
- the surface-treated steel sheet produced by the production method of the present invention has a temperature higher than the melting point temperature of tin (for example, 250), even if the resin film formed into a biaxially oriented resin film is drawn. (° C.).
- the low carbon cold-rolled steel sheet was electrolytically degreased—washed with water, washed with sulfuric acid—washed with water, and then the iron surface was exposed using a tin sulfate plating bath under the following tin plating conditions and the conditions shown in Tables 1-6.
- Metal tin was formed on the steel sheet surface.
- Example 2 [Creation of surface-treated steel sheet] Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 70 g / L Plating conditions Plating current density: 7 A / dm 2 , Plating bath temperature: 40 ° C Tin plating amount: 2.8 [Production of resin-coated steel sheet] The same operation as in Example 1 was performed.
- Example 3 [Creation of surface-treated steel sheet] Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 90 g / L Plating conditions Plating current density: 10 A / dm 2 Plating bath temperature: 40 ° C Tin plating amount: 2.8 [Production of resin-coated steel sheet] The same operation as in Example 1 was performed.
- FIG. 1 (a) is a surface observation photograph (SEM image) of a surface-treated steel sheet in a state where tin exposed from the iron surface of Example 1 of the present invention is deposited on the steel sheet surface.
- FIG. 1B is a surface observation photograph of the surface-treated steel sheet of Comparative Example 1.
- the tin plating layer exposing the iron surface having an average particle diameter of 10 ⁇ m is dispersed and precipitated in a state where the iron surface is exposed on the steel sheet where the iron base is partially exposed (exposed to the iron base).
- small metal tin particles are deposited on the steel sheet, and the ground iron is not exposed.
- ⁇ Adhesion evaluation> [Production of 1st cup]
- a resin-coated steel sheet obtained by laminating a resin film on the surface-treated steel sheet of the present invention and the comparative example After punching into a blank having a diameter of 151 mm, the transparent unstretched film-coated surface is the inner surface of the cup (the surface coated with the white unstretched film is the outer surface of the can), and the drawing ratio is 1.64.
- a step-drawing process was performed to prepare a first cup, a B / M can, and a CHS can, and a test piece for adhesion evaluation was prepared so that the transparent unstretched film-coated surface became the measurement surface.
- the cups using the resin-coated steel plates prepared from the surface-treated steel plates of Examples 1 to 3 are 1st cups, and the S peel strength is 0.25 g / 15 mm, 0.35 g / 15 mm, and 0.5 g, respectively. / 15 mm or more, showing excellent process adhesion of the resin film during can molding. Further, no delamination of the cup tip of the 1st cup, B / M can and CHS can was observed (circle mark). On the other hand, when using the resin-coated steel sheet prepared from the surface-treated steel sheet of the comparative example, when forming the 1st cup, the resin film at the tip of the cup and the surface-treated steel sheet become poor adhesion, Delamination occurred at the tip of the cup.
- the display of the plating appearance is described as “overall coating”, the condition outside the scope of the present invention was that the tin area ratio was 100% and the S peel strength was 0.02 kg / 15 mm.
- the indication of plating appearance is described as “dendritic precipitation” or “dendritic” (dendritic precipitation), but the conditions outside the scope of the present invention are in the plating state exceeding the appropriate current density range, and the metal is plated on the plating surface.
- the Sn powder is precipitated and has a black color tone, which has no commercial value.
- the tin area ratio was 100%, and the S peel strength was 0.01 kg / 15 mm.
- the notation of the upward arrow ( ⁇ ) means the same state as that described in the column above it.
- the resin-coated steel sheet using the surface-treated steel sheet manufactured by the manufacturing method of the present invention is subjected to any one of drawing, further stretching after drawing, and further ironing after drawing. Even if it is applied, the resin film does not peel off during the molding process, and the resin film is stable even during the can body molding process, which is subjected to a process that is combined with a stretch process and an ironing process after a more severe drawing process. It does not peel off and shows excellent processing adhesion stably.
- the T peel strength was measured in the state of a flat plate before processing, but it is considered that the processing adhesion is not necessarily accurately reflected.
- Adopted S peel strength as peel strength. In other words, the adhesiveness (working adhesion) during and after processing is accurate when strict forming processing is performed, such as drawing and drawing together with the ironing process after drawing. S peel strength was adopted as an evaluation method to be reflected. The S peel strength is formed by drawing a resin-coated steel sheet into a cup, cutting a specimen from the side wall of the cup, and evaluating the work adhesion strength by the peel strength of the resin film of the specimen.
- a specific method for measuring the S peel strength is shown below.
- a blank having a diameter of 154 mm is punched out of a resin-coated steel sheet, and a first-stage drawing is performed at a drawing ratio of 1.64 to form a drawn cup having a diameter of 96 mm and a height of 42 mm.
- a T-shape having a size as shown in the plan view of FIG. The test piece 71 is punched out using a press die.
- the upper part 74 b of the specimen holder 74 and the specimen 74 are arranged.
- the other end portion 71b of the piece 71 was sandwiched between the two chuck portions of the tensile tester, and the tensile strength was measured by forcibly peeling the coating resin from the surface-treated steel sheet, and this value was defined as the S peel strength.
- the S peel strength measured as described above is preferably 0.2 kg / 15 mm or more when the width of the specimen is 15 mm. If the S peel strength is less than 0.2 kg / 15 mm, stable and good working adhesion cannot be obtained in severe molding processes such as a can-making process using a stretch process and an ironing process after drawing.
- the present invention stably improves the surface-treated steel sheet with improved corrosion resistance without reducing the workability of the resin-coated steel sheet by improving the adhesion with the resin, which is a drawback of the conventional surface-treated steel sheet. It can be manufactured and has industrial value.
- Specimen 71a One end 71b of the specimen: The other end 72 of the specimen: Cut 73: Score 74: Specimen holder 74a: Specimen insertion part 74b: Upper part of the specimen holder
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Abstract
Provided is a method for producing a surface-treated steel sheet which is used in a resin-coated steel sheet and which has excellent processed adhesiveness when worked by rigorous molding. The method for producing a surface-treated steel sheet involves adjusting the Sn concentration in a tin sulfate plating bath containing sulfuric acid and tin sulfate to within a range of 30 to 120 g/L, the tin sulfate plating bath temperature to within a range of 20ºC to 60ºC, and the current density in the tin sulfate plating to within a range of 2 to 50 A/dm2, and also involves coating the steel sheet surface with metallic tin in such a way that the percentage of the steel sheet surface covered by tin is 5% to 95% and some of the iron at the steel sheet surface is exposed.
Description
本発明は、加工密着性に優れた樹脂被覆鋼板用の表面処理鋼板の製造方法に関する。
The present invention relates to a method for producing a surface-treated steel sheet for a resin-coated steel sheet having excellent work adhesion.
近年、樹脂を被覆してなる鋼板を絞り加工や絞り加工後のさらなるストレッチ加工、絞り加工後のさらなるしごき加工、絞り加工後のさらなるストレッチ加工としごき加工を併用する加工、などの厳しい加工を施してなる缶胴部と、缶底部とが一体で加工成形された缶体に天板を巻締めた缶が製造されている。これらの缶体においては、厳しい成形加工中および成形加工後に被覆樹脂が剥離もしくは破断することがないように、鋼板に対する樹脂の優れた密着性が要求される。そのため、これらの缶体用の素材として、加工密着性に優れるクロメート皮膜を表面に形成させたティンフリースチール（ＴＦＳ）などのクロメート処理鋼板に有機樹脂を被覆した樹脂被覆クロメート処理鋼板が用いられていた。
In recent years, steel plates coated with resin have been subjected to severe processing such as drawing, further stretching after drawing, further ironing after drawing, and processing that combines ironing with further stretching after drawing. A can body is manufactured by winding a top plate on a can body in which a can body portion and a can bottom portion are integrally formed. In these cans, excellent adhesion of the resin to the steel sheet is required so that the coating resin does not peel or break during or after the severe forming process. For this reason, resin-coated chromate-treated steel sheets in which an organic resin is coated on a chromate-treated steel sheet such as tin-free steel (TFS) with a chromate film having excellent processing adhesion on the surface are used as materials for these cans. It was.
しかし、樹脂被覆クロメート処理鋼板を用いた缶体においては、樹脂層に鋼板面に達する微細な孔や亀裂が生じた場合、クロメート処理鋼板が耐食性に乏しいために、特に酸性度の大きな内容物を充填した場合に、鋼板の腐食が急速に進行しやすいという問題点があった。
そのため、酸性度の大きな内容物を缶に充填した場合においても、優れた耐食性を示す錫めっき鋼板に樹脂を被覆してなる樹脂被覆錫めっき鋼板の適用が試みられたが、錫めっき層に対する樹脂の密着性、特に缶体加工時におけるフィルム加工密着性に乏しく、上記のような厳しい加工用途であってもフィルム加工密着性に優れた材料の開発が求められていた。特に、ぶりきは錫酸化膜と被覆温度が低い影響でＴＦＳよりもフィルム密着性に劣るという問題点もあった。
一般に、飲料缶に使用するめっき鋼板には主としてぶりき（錫めっき鋼板）とＴＦＳ（電解クロムめっき鋼板）が有るが、腐食性の高い内容物の充填には錫の犠牲防食作用を利用できる、ぶりきの方がＴＦＳよりも耐食性に優れている。ぶりきは錫酸化膜の存在（有機樹脂フィルムとの密着性を阻害する）と、錫の融点（２３２℃）以上での被覆が困難（錫が溶融して流動性を帯び、加熱設備に付着する）であるため、錫の融点以上での被覆が困難であり、製缶後のフィルム密着性はＴＦＳに劣るのが現状である。
一方、ＴＦＳは耐食性においてはぶりきに劣るが、表層にはフィルム密着性に優れるクロムオキサイド皮膜が存在すると共に、２３２℃以上の温度での被覆が可能であり（クロムの融点＝約１８００℃）製缶後のフィルム密着性はぶりきよりも優れる。 However, in cans using resin-coated chromate-treated steel sheets, if fine holes or cracks that reach the steel sheet surface occur in the resin layer, the chromate-treated steel sheet has poor corrosion resistance. When filled, there was a problem that the corrosion of the steel sheet was likely to proceed rapidly.
Therefore, even when filling the can with high acidity contents, application of a resin-coated tin-plated steel sheet obtained by coating a resin on a tin-plated steel sheet exhibiting excellent corrosion resistance has been attempted. Therefore, the development of a material excellent in film processing adhesion has been demanded even in severe processing applications as described above. In particular, tinplate has a problem that film adhesion is inferior to that of TFS due to the low tin oxide film and coating temperature.
In general, the plated steel sheet used for beverage cans mainly has tinplate (tin-plated steel sheet) and TFS (electrolytic chromium-plated steel sheet), but the filling of highly corrosive contents can utilize the sacrificial anticorrosive action of tin. The tinplate has better corrosion resistance than TFS. Tinplate has a tin oxide film (inhibits adhesion to the organic resin film) and is difficult to coat above the melting point of tin (232 ° C) (tin melts and becomes fluid and adheres to heating equipment) Therefore, it is difficult to cover at the melting point of tin or higher, and the film adhesion after canning is inferior to TFS.
On the other hand, TFS is inferior in tinting in corrosion resistance, but a chromium oxide film having excellent film adhesion exists on the surface layer and can be coated at a temperature of 232 ° C. or higher (melting point of chromium = about 1800 ° C.). Film adhesion after can making is better than tinplate.
そのため、酸性度の大きな内容物を缶に充填した場合においても、優れた耐食性を示す錫めっき鋼板に樹脂を被覆してなる樹脂被覆錫めっき鋼板の適用が試みられたが、錫めっき層に対する樹脂の密着性、特に缶体加工時におけるフィルム加工密着性に乏しく、上記のような厳しい加工用途であってもフィルム加工密着性に優れた材料の開発が求められていた。特に、ぶりきは錫酸化膜と被覆温度が低い影響でＴＦＳよりもフィルム密着性に劣るという問題点もあった。
一般に、飲料缶に使用するめっき鋼板には主としてぶりき（錫めっき鋼板）とＴＦＳ（電解クロムめっき鋼板）が有るが、腐食性の高い内容物の充填には錫の犠牲防食作用を利用できる、ぶりきの方がＴＦＳよりも耐食性に優れている。ぶりきは錫酸化膜の存在（有機樹脂フィルムとの密着性を阻害する）と、錫の融点（２３２℃）以上での被覆が困難（錫が溶融して流動性を帯び、加熱設備に付着する）であるため、錫の融点以上での被覆が困難であり、製缶後のフィルム密着性はＴＦＳに劣るのが現状である。
一方、ＴＦＳは耐食性においてはぶりきに劣るが、表層にはフィルム密着性に優れるクロムオキサイド皮膜が存在すると共に、２３２℃以上の温度での被覆が可能であり（クロムの融点＝約１８００℃）製缶後のフィルム密着性はぶりきよりも優れる。 However, in cans using resin-coated chromate-treated steel sheets, if fine holes or cracks that reach the steel sheet surface occur in the resin layer, the chromate-treated steel sheet has poor corrosion resistance. When filled, there was a problem that the corrosion of the steel sheet was likely to proceed rapidly.
Therefore, even when filling the can with high acidity contents, application of a resin-coated tin-plated steel sheet obtained by coating a resin on a tin-plated steel sheet exhibiting excellent corrosion resistance has been attempted. Therefore, the development of a material excellent in film processing adhesion has been demanded even in severe processing applications as described above. In particular, tinplate has a problem that film adhesion is inferior to that of TFS due to the low tin oxide film and coating temperature.
In general, the plated steel sheet used for beverage cans mainly has tinplate (tin-plated steel sheet) and TFS (electrolytic chromium-plated steel sheet), but the filling of highly corrosive contents can utilize the sacrificial anticorrosive action of tin. The tinplate has better corrosion resistance than TFS. Tinplate has a tin oxide film (inhibits adhesion to the organic resin film) and is difficult to coat above the melting point of tin (232 ° C) (tin melts and becomes fluid and adheres to heating equipment) Therefore, it is difficult to cover at the melting point of tin or higher, and the film adhesion after canning is inferior to TFS.
On the other hand, TFS is inferior in tinting in corrosion resistance, but a chromium oxide film having excellent film adhesion exists on the surface layer and can be coated at a temperature of 232 ° C. or higher (melting point of chromium = about 1800 ° C.). Film adhesion after can making is better than tinplate.
上記のような問題点を解決するため、特許文献１には、ノーリフロー錫めっき鋼板（錫溶融処理をしない錫めっき鋼板）またはリフロー錫めっき鋼板（錫溶融処理をした錫めっき鋼板）の錫めっき層上にシランカップリング剤塗布層を設け、さらに有機樹脂皮膜を積層してなる樹脂被覆錫めっき鋼板が記載されている。
In order to solve the above problems, Patent Document 1 discloses a tin plating of a no-reflow tin-plated steel sheet (tin-plated steel sheet not subjected to tin fusion treatment) or a reflow tin-plated steel sheet (tin-plated steel sheet subjected to tin fusion treatment). A resin-coated tin-plated steel sheet in which a silane coupling agent coating layer is provided on a layer and an organic resin film is further laminated is described.
しかし、特許文献１の樹脂被覆錫めっき鋼板の処理は新たな処理を付加することとなるため、ぶりきの製造コストは高くなるだけでなく、絞り加工後にさらにストレッチ加工としごき加工を併用して缶体に成形加工した場合、成形加工途中で缶体の上部で樹脂が剥離する場合があり、缶体加工時における樹脂の加工密着性に問題があった。
本発明は、上記の問題点を解決し、厳しい成形加工時においても、加工密着性に優れた樹脂被覆鋼板用の表面処理鋼板の製造方法及びその表面処理鋼板上に樹脂を被覆した樹脂被覆鋼板を提供することを目的とする。 However, since the treatment of the resin-coated tin-plated steel sheet ofPatent Document 1 adds a new treatment, not only does the manufacturing cost of the tinplate increase, but it also uses stretch and ironing in combination after drawing. In the case of molding into a can body, the resin may peel off at the upper part of the can body during the molding process, and there was a problem in the processing adhesion of the resin during can body processing.
The present invention solves the above-described problems and provides a method for producing a surface-treated steel sheet for a resin-coated steel sheet having excellent work adhesion even during severe forming, and a resin-coated steel sheet obtained by coating a resin on the surface-treated steel sheet The purpose is to provide.
本発明は、上記の問題点を解決し、厳しい成形加工時においても、加工密着性に優れた樹脂被覆鋼板用の表面処理鋼板の製造方法及びその表面処理鋼板上に樹脂を被覆した樹脂被覆鋼板を提供することを目的とする。 However, since the treatment of the resin-coated tin-plated steel sheet of
The present invention solves the above-described problems and provides a method for producing a surface-treated steel sheet for a resin-coated steel sheet having excellent work adhesion even during severe forming, and a resin-coated steel sheet obtained by coating a resin on the surface-treated steel sheet The purpose is to provide.
（１）本発明の表面処理鋼板の製造方法は、
硫酸及び硫酸錫を含む硫酸錫めっき浴中のＳｎ濃度を３０～１２０ｇ／Ｌ、
該硫酸錫めっき浴の温度を２０～６０℃、
該硫酸錫めっきにおける電流密度を２～５０Ａ／ｄｍ２、
の範囲で調整して、鋼板表面上に占める錫面積率を５～９５％とし、
鋼板表面の鉄の一部を露出させるように鋼板表面に金属錫を被覆することを特徴とする。
（２）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を３０～５０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２Ａ／ｄｍ２以下とすることを特徴とする。
（３）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を３０～５０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を４０～６０℃、
前記硫酸錫めっきにおける電流密度を２～５Ａ／ｄｍ２とすることを特徴とする。
（４）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～５Ａ／ｄｍ２とすることを特徴とする。
（５）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２～７Ａ／ｄｍ２とすることを特徴とする。
（６）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を５０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする。
（７）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～７Ａ／ｄｍ２とすることを特徴とする。
（８）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする。
（９）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を５０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１５Ａ／ｄｍ２とすることを特徴とする。
（１０）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を９０～１２０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする。
（１１）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を９０～１２０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を４０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１５Ａ／ｄｍ２とすることを特徴とする。
（１２）本発明の樹脂被覆鋼板の製造方法は、前記（１）～（１１）いずれかに記載の製造方法によって製造された表面処理鋼板上に、樹脂を被覆することを特徴とする。
（１３）本発明の樹脂被覆鋼板の製造方法は、前記（１２）において、前記樹脂被覆を錫の融点以上の温度で行うことを特徴とする。 (1) The method for producing the surface-treated steel sheet of the present invention is as follows:
Sn concentration in a tin sulfate plating bath containing sulfuric acid and tin sulfate is 30 to 120 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.
The current density in the tin sulfate plating is 2 to 50 A / dm 2 ,
In this range, the tin area ratio on the steel sheet surface is 5 to 95%,
The surface of the steel sheet is coated with metallic tin so that a part of the iron on the steel sheet surface is exposed.
(2) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 30-50 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
A current density in the tin sulfate plating is 2 A / dm 2 or less.
(3) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 30-50 g / L,
The temperature of the tin sulfate plating bath is 40-60 ° C.
The current density in the tin sulfate plating is 2 to 5 A / dm 2 .
(4) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
The current density in the tin sulfate plating is 2 to 5 A / dm 2 .
(5) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
The current density in the tin sulfate plating is 2 to 7 A / dm 2 .
(6) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 50-60 ° C.,
The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
(7) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
The current density in the tin sulfate plating is 2 to 7 A / dm 2 .
(8) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
(9) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 50-60 ° C.,
The current density in the tin sulfate plating is 2 to 15 A / dm 2 .
(10) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 90 to 120 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
(11) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 90 to 120 g / L,
The temperature of the tin sulfate plating bath is 40-60 ° C.
The current density in the tin sulfate plating is 2 to 15 A / dm 2 .
(12) The method for producing a resin-coated steel sheet according to the present invention is characterized in that a resin is coated on the surface-treated steel sheet produced by the production method described in any one of (1) to (11).
(13) The method for producing a resin-coated steel sheet according to the present invention is characterized in that, in (12), the resin coating is performed at a temperature equal to or higher than a melting point of tin.
硫酸及び硫酸錫を含む硫酸錫めっき浴中のＳｎ濃度を３０～１２０ｇ／Ｌ、
該硫酸錫めっき浴の温度を２０～６０℃、
該硫酸錫めっきにおける電流密度を２～５０Ａ／ｄｍ２、
の範囲で調整して、鋼板表面上に占める錫面積率を５～９５％とし、
鋼板表面の鉄の一部を露出させるように鋼板表面に金属錫を被覆することを特徴とする。
（２）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を３０～５０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２Ａ／ｄｍ２以下とすることを特徴とする。
（３）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を３０～５０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を４０～６０℃、
前記硫酸錫めっきにおける電流密度を２～５Ａ／ｄｍ２とすることを特徴とする。
（４）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～５Ａ／ｄｍ２とすることを特徴とする。
（５）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２～７Ａ／ｄｍ２とすることを特徴とする。
（６）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を５０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする。
（７）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～７Ａ／ｄｍ２とすることを特徴とする。
（８）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする。
（９）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を５０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１５Ａ／ｄｍ２とすることを特徴とする。
（１０）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を９０～１２０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする。
（１１）本発明の表面処理鋼板の製造方法は、前記（１）において、
前記硫酸錫めっき浴中のＳｎ濃度を９０～１２０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を４０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１５Ａ／ｄｍ２とすることを特徴とする。
（１２）本発明の樹脂被覆鋼板の製造方法は、前記（１）～（１１）いずれかに記載の製造方法によって製造された表面処理鋼板上に、樹脂を被覆することを特徴とする。
（１３）本発明の樹脂被覆鋼板の製造方法は、前記（１２）において、前記樹脂被覆を錫の融点以上の温度で行うことを特徴とする。 (1) The method for producing the surface-treated steel sheet of the present invention is as follows:
Sn concentration in a tin sulfate plating bath containing sulfuric acid and tin sulfate is 30 to 120 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.
The current density in the tin sulfate plating is 2 to 50 A / dm 2 ,
In this range, the tin area ratio on the steel sheet surface is 5 to 95%,
The surface of the steel sheet is coated with metallic tin so that a part of the iron on the steel sheet surface is exposed.
(2) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 30-50 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
A current density in the tin sulfate plating is 2 A / dm 2 or less.
(3) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 30-50 g / L,
The temperature of the tin sulfate plating bath is 40-60 ° C.
The current density in the tin sulfate plating is 2 to 5 A / dm 2 .
(4) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
The current density in the tin sulfate plating is 2 to 5 A / dm 2 .
(5) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
The current density in the tin sulfate plating is 2 to 7 A / dm 2 .
(6) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 50-60 ° C.,
The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
(7) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
The current density in the tin sulfate plating is 2 to 7 A / dm 2 .
(8) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
(9) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 50-60 ° C.,
The current density in the tin sulfate plating is 2 to 15 A / dm 2 .
(10) In the manufacturing method of the surface-treated steel sheet of the present invention,
Sn concentration in the tin sulfate plating bath is 90 to 120 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
The current density in the tin sulfate plating is 2 to 10 A / dm 2 .
(11) The method for producing a surface-treated steel sheet according to the present invention is as described in (1) above.
Sn concentration in the tin sulfate plating bath is 90 to 120 g / L,
The temperature of the tin sulfate plating bath is 40-60 ° C.
The current density in the tin sulfate plating is 2 to 15 A / dm 2 .
(12) The method for producing a resin-coated steel sheet according to the present invention is characterized in that a resin is coated on the surface-treated steel sheet produced by the production method described in any one of (1) to (11).
(13) The method for producing a resin-coated steel sheet according to the present invention is characterized in that, in (12), the resin coating is performed at a temperature equal to or higher than a melting point of tin.
本発明によれば、鋼板表面の鉄の一部を露出させて錫を被覆するので、その上に樹脂層を積層させた樹脂被覆鋼板は、従来よりも優れた加工密着性を示す。
また、鋼板表面の鉄の一部を露出させて錫を被覆するので、その上に積層させた樹脂層は密着性の良好な鉄面と接着すると同時に、凹凸によるアンカー効果で従来のフラットな表面の錫めっき鋼板よりも樹脂層との密着性を大幅に向上させることができる。
また、鉄の一部を露出させて錫を被覆した表面処理鋼板は錫の融点（２３２℃）以上の温度で樹脂被覆をすることが可能であり、製缶後の樹脂層の密着性もＴＦＳ並の優れた密着性を示す。
すなわち、従来の錫めっき鋼板はその表面全面に錫が存在するため、錫の融点以上で樹脂被覆を行うと、錫溶融処理時に溶融した錫が流動性を有し、外観が不均一になると同時に、樹脂被覆時に加熱設備に錫が付着するなどの弊害が生じるため錫の融点以上の被覆は困難であったが、本発明の製造方法によって形成される鉄の一部を露出させて錫を被覆した表面処理鋼板は、錫の融点以上の温度に加熱しても、溶融した錫同士が結合せず流動性を有しないため、錫の融点以上での樹脂被覆が可能となる。
さらに、本発明の表面処理鋼板の製造方法は、硫酸錫めっき浴を用いることができ、この浴は、従来のフェロスタン錫めっき浴成分のＰＳＡ（フェノールスルフォン酸）ではなく、安価な硫酸を用いるため、めっき浴のコストダウン、およびＣＯＤの低減にも繋がる。 According to the present invention, since a part of iron on the surface of the steel sheet is exposed and coated with tin, the resin-coated steel sheet having a resin layer laminated thereon exhibits a work adhesion superior to that of the prior art.
In addition, since a part of iron on the steel plate surface is exposed and covered with tin, the resin layer laminated thereon adheres to the iron surface with good adhesion, and at the same time, a conventional flat surface with an anchor effect due to unevenness As compared with the tin-plated steel sheet, the adhesion with the resin layer can be greatly improved.
Further, a surface-treated steel sheet in which a part of iron is exposed and coated with tin can be coated with resin at a temperature equal to or higher than the melting point of tin (232 ° C.), and the adhesion of the resin layer after canning is also TFS. Shows excellent adhesion.
That is, since tin is present on the entire surface of conventional tin-plated steel sheet, when the resin coating is performed at a temperature higher than the melting point of tin, the molten tin at the time of the tin melting process has fluidity and the appearance becomes uneven. However, it was difficult to cover the melting point of tin because of the harmful effect of tin adhering to the heating equipment at the time of resin coating, but it was covered with tin by exposing part of the iron formed by the manufacturing method of the present invention. Even if the surface-treated steel sheet is heated to a temperature equal to or higher than the melting point of tin, the melted tin does not bond to each other and does not have fluidity.
Furthermore, the manufacturing method of the surface-treated steel sheet of the present invention can use a tin sulfate plating bath, and this bath uses inexpensive sulfuric acid instead of PSA (phenol sulfonic acid) which is a conventional ferrostantin plating bath component. , Leading to cost reduction of the plating bath and reduction of COD.
また、鋼板表面の鉄の一部を露出させて錫を被覆するので、その上に積層させた樹脂層は密着性の良好な鉄面と接着すると同時に、凹凸によるアンカー効果で従来のフラットな表面の錫めっき鋼板よりも樹脂層との密着性を大幅に向上させることができる。
また、鉄の一部を露出させて錫を被覆した表面処理鋼板は錫の融点（２３２℃）以上の温度で樹脂被覆をすることが可能であり、製缶後の樹脂層の密着性もＴＦＳ並の優れた密着性を示す。
すなわち、従来の錫めっき鋼板はその表面全面に錫が存在するため、錫の融点以上で樹脂被覆を行うと、錫溶融処理時に溶融した錫が流動性を有し、外観が不均一になると同時に、樹脂被覆時に加熱設備に錫が付着するなどの弊害が生じるため錫の融点以上の被覆は困難であったが、本発明の製造方法によって形成される鉄の一部を露出させて錫を被覆した表面処理鋼板は、錫の融点以上の温度に加熱しても、溶融した錫同士が結合せず流動性を有しないため、錫の融点以上での樹脂被覆が可能となる。
さらに、本発明の表面処理鋼板の製造方法は、硫酸錫めっき浴を用いることができ、この浴は、従来のフェロスタン錫めっき浴成分のＰＳＡ（フェノールスルフォン酸）ではなく、安価な硫酸を用いるため、めっき浴のコストダウン、およびＣＯＤの低減にも繋がる。 According to the present invention, since a part of iron on the surface of the steel sheet is exposed and coated with tin, the resin-coated steel sheet having a resin layer laminated thereon exhibits a work adhesion superior to that of the prior art.
In addition, since a part of iron on the steel plate surface is exposed and covered with tin, the resin layer laminated thereon adheres to the iron surface with good adhesion, and at the same time, a conventional flat surface with an anchor effect due to unevenness As compared with the tin-plated steel sheet, the adhesion with the resin layer can be greatly improved.
Further, a surface-treated steel sheet in which a part of iron is exposed and coated with tin can be coated with resin at a temperature equal to or higher than the melting point of tin (232 ° C.), and the adhesion of the resin layer after canning is also TFS. Shows excellent adhesion.
That is, since tin is present on the entire surface of conventional tin-plated steel sheet, when the resin coating is performed at a temperature higher than the melting point of tin, the molten tin at the time of the tin melting process has fluidity and the appearance becomes uneven. However, it was difficult to cover the melting point of tin because of the harmful effect of tin adhering to the heating equipment at the time of resin coating, but it was covered with tin by exposing part of the iron formed by the manufacturing method of the present invention. Even if the surface-treated steel sheet is heated to a temperature equal to or higher than the melting point of tin, the melted tin does not bond to each other and does not have fluidity.
Furthermore, the manufacturing method of the surface-treated steel sheet of the present invention can use a tin sulfate plating bath, and this bath uses inexpensive sulfuric acid instead of PSA (phenol sulfonic acid) which is a conventional ferrostantin plating bath component. , Leading to cost reduction of the plating bath and reduction of COD.
以下、本発明の実施の形態について詳細に説明する。
［鋼板］
本発明の表面処理鋼板の原板として用いる鋼板としては、一般的に缶用に用いられている低炭素アルミキルド熱間圧延板を焼鈍した後、調質圧延した板厚＝０．１５～０．３ｍｍの冷延鋼板や、焼鈍後さらに冷間圧延を施して強度を増加させた冷延鋼板等が、用途に応じて用いられる。また、ニオブ、チタンを添加した非時効性極低炭素鋼から製造した冷延鋼板も適用可能である。これらの冷延鋼板を電解脱脂し酸洗した後、鋼板上に錫めっき層を形成させて表面処理鋼板とする。 Hereinafter, embodiments of the present invention will be described in detail.
[steel sheet]
The steel sheet used as the original sheet of the surface-treated steel sheet of the present invention is a sheet thickness of 0.15 to 0.3 mm after annealing a low carbon aluminum killed hot rolled sheet generally used for cans. A cold-rolled steel sheet, a cold-rolled steel sheet that has been further cold-rolled after annealing to increase its strength, and the like are used depending on the application. Further, a cold-rolled steel sheet manufactured from non-aging ultra-low carbon steel added with niobium and titanium is also applicable. After these cold-rolled steel sheets are electrolytically degreased and pickled, a tin-plated layer is formed on the steel sheets to obtain surface-treated steel sheets.
［鋼板］
本発明の表面処理鋼板の原板として用いる鋼板としては、一般的に缶用に用いられている低炭素アルミキルド熱間圧延板を焼鈍した後、調質圧延した板厚＝０．１５～０．３ｍｍの冷延鋼板や、焼鈍後さらに冷間圧延を施して強度を増加させた冷延鋼板等が、用途に応じて用いられる。また、ニオブ、チタンを添加した非時効性極低炭素鋼から製造した冷延鋼板も適用可能である。これらの冷延鋼板を電解脱脂し酸洗した後、鋼板上に錫めっき層を形成させて表面処理鋼板とする。 Hereinafter, embodiments of the present invention will be described in detail.
[steel sheet]
The steel sheet used as the original sheet of the surface-treated steel sheet of the present invention is a sheet thickness of 0.15 to 0.3 mm after annealing a low carbon aluminum killed hot rolled sheet generally used for cans. A cold-rolled steel sheet, a cold-rolled steel sheet that has been further cold-rolled after annealing to increase its strength, and the like are used depending on the application. Further, a cold-rolled steel sheet manufactured from non-aging ultra-low carbon steel added with niobium and titanium is also applicable. After these cold-rolled steel sheets are electrolytically degreased and pickled, a tin-plated layer is formed on the steel sheets to obtain surface-treated steel sheets.
［めっき浴］
表面処理鋼板は、本発明においては、硫酸錫めっき浴を用いる。
硫酸錫めっき浴の組成としては、
硫酸錫濃度（Ｓｎ濃度として）：３０～１２０ｇ／Ｌ、
その他、界面活性剤や酸化防止剤なども添加することができる。
めっき条件としては、
めっき電流密度：２～５０Ａ／ｄｍ２、
めっき浴温度：２０～６０℃、の範囲とする。
硫酸錫濃度がＳｎ濃度として３０ｇ／Ｌ未満である場合は、
電流密度を下げてもＳｎの析出形態が、地鉄が露出されている状態（地鉄露出）にならず、樹脂を被覆した場合に密着性が向上しない。
一方、硫酸錫濃度（Ｓｎ濃度として）１２０ｇ／Ｌを超える場合は、濃度が変動しやすく正確なめっき操作が困難な場合がある。また、ｐＨが低くなりすぎ、めっき液の腐食性が高くなりめっき液が汚染される可能性がある。
めっき電流密度：２～５０Ａ／ｄｍ２とした理由は、２Ａ／ｄｍ２未満だとめっき処理終了までに長時間を要してしまい、めっき液成分の変動等により正確なめっき操作が困難な場合がある。
一方、５０Ａ／ｄｍ２を超えると全面被覆のめっきとなってしまい下地の鉄露出が無くなる。
めっき浴温度：２０～６０℃とした理由は、２０℃未満では表層錫面積率が９５％以上となり、全面被覆（下地の鉄露出なし）に近い状態となり、フィルム未着力が著しく低下する。
一方、６０℃を超えるとめっき液中の成分の濃度が変動しやすく正確なめっきが困難である。 [Plating bath]
The surface-treated steel sheet uses a tin sulfate plating bath in the present invention.
As a composition of the tin sulfate plating bath,
Tin sulfate concentration (as Sn concentration): 30 to 120 g / L,
In addition, surfactants and antioxidants can be added.
As plating conditions,
Plating current density: 2 to 50 A / dm 2
Plating bath temperature: 20 to 60 ° C.
When the tin sulfate concentration is less than 30 g / L as the Sn concentration,
Even if the current density is lowered, the Sn precipitation form does not become a state where the ground iron is exposed (ground steel exposed), and adhesion is not improved when the resin is coated.
On the other hand, when the tin sulfate concentration (Sn concentration) exceeds 120 g / L, the concentration is likely to fluctuate and accurate plating operation may be difficult. Further, the pH becomes too low, and the corrosiveness of the plating solution becomes high, which may contaminate the plating solution.
Plating current density: 2 to 50 A / dm 2 is less than 2 A / dm 2 because it takes a long time to finish the plating process, and accurate plating operation is difficult due to variations in plating solution components There is.
On the other hand, if it exceeds 50 A / dm 2 , the entire surface is plated and the underlying iron is not exposed.
The reason for the plating bath temperature: 20 to 60 ° C. is that when the temperature is lower than 20 ° C., the surface tin area ratio is 95% or more, and it is close to the entire surface coating (no underlying iron exposed), and the film non-adhesion is significantly reduced.
On the other hand, when the temperature exceeds 60 ° C., the concentration of components in the plating solution tends to fluctuate, and accurate plating is difficult.
表面処理鋼板は、本発明においては、硫酸錫めっき浴を用いる。
硫酸錫めっき浴の組成としては、
硫酸錫濃度（Ｓｎ濃度として）：３０～１２０ｇ／Ｌ、
その他、界面活性剤や酸化防止剤なども添加することができる。
めっき条件としては、
めっき電流密度：２～５０Ａ／ｄｍ２、
めっき浴温度：２０～６０℃、の範囲とする。
硫酸錫濃度がＳｎ濃度として３０ｇ／Ｌ未満である場合は、
電流密度を下げてもＳｎの析出形態が、地鉄が露出されている状態（地鉄露出）にならず、樹脂を被覆した場合に密着性が向上しない。
一方、硫酸錫濃度（Ｓｎ濃度として）１２０ｇ／Ｌを超える場合は、濃度が変動しやすく正確なめっき操作が困難な場合がある。また、ｐＨが低くなりすぎ、めっき液の腐食性が高くなりめっき液が汚染される可能性がある。
めっき電流密度：２～５０Ａ／ｄｍ２とした理由は、２Ａ／ｄｍ２未満だとめっき処理終了までに長時間を要してしまい、めっき液成分の変動等により正確なめっき操作が困難な場合がある。
一方、５０Ａ／ｄｍ２を超えると全面被覆のめっきとなってしまい下地の鉄露出が無くなる。
めっき浴温度：２０～６０℃とした理由は、２０℃未満では表層錫面積率が９５％以上となり、全面被覆（下地の鉄露出なし）に近い状態となり、フィルム未着力が著しく低下する。
一方、６０℃を超えるとめっき液中の成分の濃度が変動しやすく正確なめっきが困難である。 [Plating bath]
The surface-treated steel sheet uses a tin sulfate plating bath in the present invention.
As a composition of the tin sulfate plating bath,
Tin sulfate concentration (as Sn concentration): 30 to 120 g / L,
In addition, surfactants and antioxidants can be added.
As plating conditions,
Plating current density: 2 to 50 A / dm 2
Plating bath temperature: 20 to 60 ° C.
When the tin sulfate concentration is less than 30 g / L as the Sn concentration,
Even if the current density is lowered, the Sn precipitation form does not become a state where the ground iron is exposed (ground steel exposed), and adhesion is not improved when the resin is coated.
On the other hand, when the tin sulfate concentration (Sn concentration) exceeds 120 g / L, the concentration is likely to fluctuate and accurate plating operation may be difficult. Further, the pH becomes too low, and the corrosiveness of the plating solution becomes high, which may contaminate the plating solution.
Plating current density: 2 to 50 A / dm 2 is less than 2 A / dm 2 because it takes a long time to finish the plating process, and accurate plating operation is difficult due to variations in plating solution components There is.
On the other hand, if it exceeds 50 A / dm 2 , the entire surface is plated and the underlying iron is not exposed.
The reason for the plating bath temperature: 20 to 60 ° C. is that when the temperature is lower than 20 ° C., the surface tin area ratio is 95% or more, and it is close to the entire surface coating (no underlying iron exposed), and the film non-adhesion is significantly reduced.
On the other hand, when the temperature exceeds 60 ° C., the concentration of components in the plating solution tends to fluctuate, and accurate plating is difficult.
［表面錫面積率］
鋼板上に分散して析出させる金属錫の鋼板上で占める面積、すなわち表面錫面積率は、５～９５％とすることが望ましい。
表面錫面積率が５％未満では、耐食性や加工性が著しく悪くなるので、少なくとも５％以上の錫面積率が必要である。
表面錫面積率が９５％を超えると、鉄の露出面積が少なくなり、樹脂層の密着性向上に寄与しない。樹脂層との密着性向上のためには、少なくとも鉄の露出面積が５％以上必要であるからである。
この鋼板上の表面錫面積率は、表面を電子顕微鏡で観察したものを第１画像とし、鋼板表面上に分散し存在する錫を化学的に除去した後、再度電子顕微鏡写真で観察したものを第２画像とし、得られた両画像をコンピュータ画像処理によって比較することによって求めることができる。 [Surface tin area ratio]
The area occupied on the steel plate by the metal tin dispersed and deposited on the steel plate, that is, the surface tin area ratio, is preferably 5 to 95%.
If the surface tin area ratio is less than 5%, the corrosion resistance and workability are remarkably deteriorated, so a tin area ratio of at least 5% is required.
When the surface tin area ratio exceeds 95%, the exposed area of iron is reduced and does not contribute to the improvement of the adhesion of the resin layer. This is because at least 5% or more of the exposed area of iron is required to improve the adhesion with the resin layer.
The surface tin area ratio on this steel sheet is the one observed by the electron microscope, the first image, and the tin dispersed and present on the steel sheet surface was chemically removed, and then observed again by the electron micrograph. The second image can be obtained by comparing both obtained images by computer image processing.
鋼板上に分散して析出させる金属錫の鋼板上で占める面積、すなわち表面錫面積率は、５～９５％とすることが望ましい。
表面錫面積率が５％未満では、耐食性や加工性が著しく悪くなるので、少なくとも５％以上の錫面積率が必要である。
表面錫面積率が９５％を超えると、鉄の露出面積が少なくなり、樹脂層の密着性向上に寄与しない。樹脂層との密着性向上のためには、少なくとも鉄の露出面積が５％以上必要であるからである。
この鋼板上の表面錫面積率は、表面を電子顕微鏡で観察したものを第１画像とし、鋼板表面上に分散し存在する錫を化学的に除去した後、再度電子顕微鏡写真で観察したものを第２画像とし、得られた両画像をコンピュータ画像処理によって比較することによって求めることができる。 [Surface tin area ratio]
The area occupied on the steel plate by the metal tin dispersed and deposited on the steel plate, that is, the surface tin area ratio, is preferably 5 to 95%.
If the surface tin area ratio is less than 5%, the corrosion resistance and workability are remarkably deteriorated, so a tin area ratio of at least 5% is required.
When the surface tin area ratio exceeds 95%, the exposed area of iron is reduced and does not contribute to the improvement of the adhesion of the resin layer. This is because at least 5% or more of the exposed area of iron is required to improve the adhesion with the resin layer.
The surface tin area ratio on this steel sheet is the one observed by the electron microscope, the first image, and the tin dispersed and present on the steel sheet surface was chemically removed, and then observed again by the electron micrograph. The second image can be obtained by comparing both obtained images by computer image processing.
［金属錫の錫めっき量］
鋼板表面上の金属錫の錫めっき量は、５％以上の面積で鉄表面を露出させる観点から、０．１～１３ｇ／ｍ２の範囲とすることが望ましい。
好ましくは、０．５～５．６ｇ／ｍ２である。錫めっき量が０．１ｇ／ｍ２未満では、耐食性が不足するので好ましくない。特に、錫溶融（リフロー）処理を行うと、めっきした錫の全てがＦｅ－Ｓｎ合金化し、耐食性だけでなく、加工性も著しく悪くなるので、少なくとも０．１ｇ／ｍ２以上の錫めっき量を必要とする。
一方、１３ｇ／ｍ２を超えると、鉄が表面に露出されなくなり、樹脂層の密着性向上に寄与しない。 [Tin plating amount of metallic tin]
The tin plating amount of metallic tin on the steel sheet surface is preferably in the range of 0.1 to 13 g / m 2 from the viewpoint of exposing the iron surface in an area of 5% or more.
Preferably, it is 0.5 to 5.6 g / m 2 . If the tin plating amount is less than 0.1 g / m 2 , the corrosion resistance is insufficient, which is not preferable. In particular, when tin melting (reflow) treatment is performed, all of the plated tin becomes an Fe—Sn alloy, and not only the corrosion resistance but also the workability is remarkably deteriorated. Therefore, a tin plating amount of at least 0.1 g / m 2 or more is required. I need.
On the other hand, when it exceeds 13 g / m 2 , iron is not exposed to the surface, and does not contribute to the improvement of the adhesion of the resin layer.
鋼板表面上の金属錫の錫めっき量は、５％以上の面積で鉄表面を露出させる観点から、０．１～１３ｇ／ｍ２の範囲とすることが望ましい。
好ましくは、０．５～５．６ｇ／ｍ２である。錫めっき量が０．１ｇ／ｍ２未満では、耐食性が不足するので好ましくない。特に、錫溶融（リフロー）処理を行うと、めっきした錫の全てがＦｅ－Ｓｎ合金化し、耐食性だけでなく、加工性も著しく悪くなるので、少なくとも０．１ｇ／ｍ２以上の錫めっき量を必要とする。
一方、１３ｇ／ｍ２を超えると、鉄が表面に露出されなくなり、樹脂層の密着性向上に寄与しない。 [Tin plating amount of metallic tin]
The tin plating amount of metallic tin on the steel sheet surface is preferably in the range of 0.1 to 13 g / m 2 from the viewpoint of exposing the iron surface in an area of 5% or more.
Preferably, it is 0.5 to 5.6 g / m 2 . If the tin plating amount is less than 0.1 g / m 2 , the corrosion resistance is insufficient, which is not preferable. In particular, when tin melting (reflow) treatment is performed, all of the plated tin becomes an Fe—Sn alloy, and not only the corrosion resistance but also the workability is remarkably deteriorated. Therefore, a tin plating amount of at least 0.1 g / m 2 or more is required. I need.
On the other hand, when it exceeds 13 g / m 2 , iron is not exposed to the surface, and does not contribute to the improvement of the adhesion of the resin layer.
［鉄表面を露出させた錫被覆］
鋼板上にめっきした錫が鉄表面を露出した状態になる理由はよく解明されていないが、酸化膜が形成された鉄表面上に、少量の錫めっきをした場合、錫の濡れ性が、鉄酸化膜の部分部分で異なるため一様な厚みの錫めっき層が形成されにくいものと考えられる。
また、金属錫の平均粒子サイズ（平面からみた粒子径の平均径）は、０．５～５０μｍとすることが望ましい。
好ましくは、２～２０μｍとする。０．５μｍ未満では粒子サイズが小さすぎて、凹凸による樹脂層のアンカー効果が充分得られず、樹脂層の密着性向上に寄与しない。
一方、平均粒子サイズが５０μｍを超える場合は、電解処理上の制約から錫の電着が困難となる。 [Tin coating with exposed iron surface]
The reason why the tin plated on the steel sheet exposes the iron surface is not well understood, but when a small amount of tin is plated on the iron surface on which the oxide film is formed, the wettability of tin is It is considered that it is difficult to form a tin plating layer having a uniform thickness because it is different in the oxide film portion.
Further, the average particle size of metal tin (the average particle size as seen from the plane) is desirably 0.5 to 50 μm.
Preferably, the thickness is 2 to 20 μm. If the particle size is less than 0.5 μm, the particle size is too small, and the anchor effect of the resin layer due to the unevenness cannot be sufficiently obtained, which does not contribute to the improvement of the adhesion of the resin layer.
On the other hand, when the average particle size exceeds 50 μm, it is difficult to deposit tin due to restrictions on electrolytic treatment.
鋼板上にめっきした錫が鉄表面を露出した状態になる理由はよく解明されていないが、酸化膜が形成された鉄表面上に、少量の錫めっきをした場合、錫の濡れ性が、鉄酸化膜の部分部分で異なるため一様な厚みの錫めっき層が形成されにくいものと考えられる。
また、金属錫の平均粒子サイズ（平面からみた粒子径の平均径）は、０．５～５０μｍとすることが望ましい。
好ましくは、２～２０μｍとする。０．５μｍ未満では粒子サイズが小さすぎて、凹凸による樹脂層のアンカー効果が充分得られず、樹脂層の密着性向上に寄与しない。
一方、平均粒子サイズが５０μｍを超える場合は、電解処理上の制約から錫の電着が困難となる。 [Tin coating with exposed iron surface]
The reason why the tin plated on the steel sheet exposes the iron surface is not well understood, but when a small amount of tin is plated on the iron surface on which the oxide film is formed, the wettability of tin is It is considered that it is difficult to form a tin plating layer having a uniform thickness because it is different in the oxide film portion.
Further, the average particle size of metal tin (the average particle size as seen from the plane) is desirably 0.5 to 50 μm.
Preferably, the thickness is 2 to 20 μm. If the particle size is less than 0.5 μm, the particle size is too small, and the anchor effect of the resin layer due to the unevenness cannot be sufficiently obtained, which does not contribute to the improvement of the adhesion of the resin layer.
On the other hand, when the average particle size exceeds 50 μm, it is difficult to deposit tin due to restrictions on electrolytic treatment.
［樹脂層の積層］
上記のようにして製造された表面処理鋼板の片面または両面に、樹脂層となる樹脂フィルムを積層する。樹脂層としては、加熱後も加工性に優れる熱可塑性樹脂が好ましく、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、エチレンテレフタレート・エチレンイソフタレート共重合体、ブチレンテレフタレート・ブチレンイソフタレート共重合体などのポリエステル樹脂、あるいはこれらのポリエステル樹脂の２種類以上をブレンドした樹脂、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体、およびそれらをマレイン酸変性したもの、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体などのポリオレフィン樹脂、６－ナイロン、６，６－ナイロン、６，１０－ナイロンなどのポリアミド樹脂、ポリカーボネート、ポリメチルペンテン、さらに上記のポリエステル樹脂とアイオノマーをブレンドしたものからなる単層の樹脂層、さらにこれらの樹脂の２種類以上からなる複層の樹脂層などが挙げられる。 [Lamination of resin layer]
The resin film used as a resin layer is laminated | stacked on the single side | surface or both surfaces of the surface treatment steel plate manufactured as mentioned above. As the resin layer, a thermoplastic resin excellent in processability after heating is preferable, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene terephthalate / ethylene isophthalate copolymer, butylene terephthalate / butylene isophthalate copolymer, etc. Polyester resin, or a blend of two or more of these polyester resins, polyethylene, polypropylene, ethylene / propylene copolymer, and those modified with maleic acid, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer Polyolefin resins such as polymers, polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon, polycarbonate, polymethylpentene, and polyester resins described above Resin layer of a single layer consisting of a blend of ionomer, and a further resin layer of the multi-layer consisting of two or more kinds of these resins.
上記のようにして製造された表面処理鋼板の片面または両面に、樹脂層となる樹脂フィルムを積層する。樹脂層としては、加熱後も加工性に優れる熱可塑性樹脂が好ましく、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、エチレンテレフタレート・エチレンイソフタレート共重合体、ブチレンテレフタレート・ブチレンイソフタレート共重合体などのポリエステル樹脂、あるいはこれらのポリエステル樹脂の２種類以上をブレンドした樹脂、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体、およびそれらをマレイン酸変性したもの、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸共重合体などのポリオレフィン樹脂、６－ナイロン、６，６－ナイロン、６，１０－ナイロンなどのポリアミド樹脂、ポリカーボネート、ポリメチルペンテン、さらに上記のポリエステル樹脂とアイオノマーをブレンドしたものからなる単層の樹脂層、さらにこれらの樹脂の２種類以上からなる複層の樹脂層などが挙げられる。 [Lamination of resin layer]
The resin film used as a resin layer is laminated | stacked on the single side | surface or both surfaces of the surface treatment steel plate manufactured as mentioned above. As the resin layer, a thermoplastic resin excellent in processability after heating is preferable, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene terephthalate / ethylene isophthalate copolymer, butylene terephthalate / butylene isophthalate copolymer, etc. Polyester resin, or a blend of two or more of these polyester resins, polyethylene, polypropylene, ethylene / propylene copolymer, and those modified with maleic acid, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer Polyolefin resins such as polymers, polyamide resins such as 6-nylon, 6,6-nylon, and 6,10-nylon, polycarbonate, polymethylpentene, and polyester resins described above Resin layer of a single layer consisting of a blend of ionomer, and a further resin layer of the multi-layer consisting of two or more kinds of these resins.
樹脂層の厚さとしては、樹脂層積層作業のしやすさ、樹脂被覆鋼板の成形加工した後の成形体（缶など）における樹脂層の表面処理鋼板との密着強度、耐食性および経済性等の観点から１０～１００μｍであることが好ましい。
これらの樹脂層は、樹脂ペレットを加熱溶融し、それを押出機のＴダイから押し出して所望の厚さのフィルムに製膜したものを、鉄表面を露出した金属錫が形成されている表面処理鋼板上に積層することによって形成される。
この樹脂層の積層方法としては例えば熱接着法が挙げられ、樹脂フィルムを、所定の温度範囲に加熱した表面処理鋼板に樹脂フィルムを当接するとともに、１対の加圧ロールで両面から挟み付けて加圧して接合する。
なお、本発明の製造方法によって製造された表面処理鋼板には、製膜した樹脂フィルムを延伸加工を施して二軸配向とした樹脂フィルムであっても、錫の融点温度より高い温度（例えば２５０℃）で熱接着することができる。 The thickness of the resin layer includes the ease of resin layer laminating work, the adhesion strength of the resin layer to the surface-treated steel sheet in a molded body (such as a can) after the resin-coated steel sheet is formed, corrosion resistance, and economic efficiency. From the viewpoint, it is preferably 10 to 100 μm.
These resin layers are heat-melted resin pellets, extruded from a T-die of an extruder to form a film with a desired thickness, and surface treatment on which metal tin with an exposed iron surface is formed It is formed by laminating on a steel plate.
As a method for laminating the resin layer, for example, a thermal bonding method is used. The resin film is brought into contact with a surface-treated steel sheet heated to a predetermined temperature range, and sandwiched from both sides with a pair of pressure rolls. Press to join.
Note that the surface-treated steel sheet produced by the production method of the present invention has a temperature higher than the melting point temperature of tin (for example, 250), even if the resin film formed into a biaxially oriented resin film is drawn. (° C.).
これらの樹脂層は、樹脂ペレットを加熱溶融し、それを押出機のＴダイから押し出して所望の厚さのフィルムに製膜したものを、鉄表面を露出した金属錫が形成されている表面処理鋼板上に積層することによって形成される。
この樹脂層の積層方法としては例えば熱接着法が挙げられ、樹脂フィルムを、所定の温度範囲に加熱した表面処理鋼板に樹脂フィルムを当接するとともに、１対の加圧ロールで両面から挟み付けて加圧して接合する。
なお、本発明の製造方法によって製造された表面処理鋼板には、製膜した樹脂フィルムを延伸加工を施して二軸配向とした樹脂フィルムであっても、錫の融点温度より高い温度（例えば２５０℃）で熱接着することができる。 The thickness of the resin layer includes the ease of resin layer laminating work, the adhesion strength of the resin layer to the surface-treated steel sheet in a molded body (such as a can) after the resin-coated steel sheet is formed, corrosion resistance, and economic efficiency. From the viewpoint, it is preferably 10 to 100 μm.
These resin layers are heat-melted resin pellets, extruded from a T-die of an extruder to form a film with a desired thickness, and surface treatment on which metal tin with an exposed iron surface is formed It is formed by laminating on a steel plate.
As a method for laminating the resin layer, for example, a thermal bonding method is used. The resin film is brought into contact with a surface-treated steel sheet heated to a predetermined temperature range, and sandwiched from both sides with a pair of pressure rolls. Press to join.
Note that the surface-treated steel sheet produced by the production method of the present invention has a temperature higher than the melting point temperature of tin (for example, 250), even if the resin film formed into a biaxially oriented resin film is drawn. (° C.).
以下、本発明を、実施例及び比較例を用いて具体的に説明する。
低炭素冷延鋼板をアルカリ水溶液中で電解脱脂－水洗、硫酸酸洗－水洗した後、硫酸錫めっき浴を用い、下記に示す錫めっき条件及び表１～６に示す条件で鉄表面を露出した金属錫を鋼板表面に形成した。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
The low carbon cold-rolled steel sheet was electrolytically degreased—washed with water, washed with sulfuric acid—washed with water, and then the iron surface was exposed using a tin sulfate plating bath under the following tin plating conditions and the conditions shown in Tables 1-6. Metal tin was formed on the steel sheet surface.
低炭素冷延鋼板をアルカリ水溶液中で電解脱脂－水洗、硫酸酸洗－水洗した後、硫酸錫めっき浴を用い、下記に示す錫めっき条件及び表１～６に示す条件で鉄表面を露出した金属錫を鋼板表面に形成した。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
The low carbon cold-rolled steel sheet was electrolytically degreased—washed with water, washed with sulfuric acid—washed with water, and then the iron surface was exposed using a tin sulfate plating bath under the following tin plating conditions and the conditions shown in Tables 1-6. Metal tin was formed on the steel sheet surface.
＜実施例１＞
［表面処理鋼板の作成］
硫酸錫めっき組成
硫酸錫濃度（Ｓｎ濃度として）：５０ｇ／Ｌ
めっき条件
めっき電流密度：５Ａ／ｄｍ２、
めっき浴温度：４０℃、
錫めっき量：２．８
［樹脂被覆鋼板の作成］
次に、上記表面処理鋼板の片面（缶内面側になる面）に、エチレンテレフタレート・エチレンイソフタレート共重合体（ＰＥＴＩ）の厚さ２８μｍの透明無延伸フィルムを積層するとともに、他の片面（缶外面側になる面）に、エチレンテレフタレート・エチレンイソフタレート共重合体（ＰＥＴＩ）にチタン系白色顔料を２０質量％含有させた白色の厚さ１６μｍのホワイト無延伸フィルムを、ラミネート温度２３０℃にて積層し、樹脂フィルムの積層終了後は直ちに冷却して樹脂被覆鋼板を作成した。 <Example 1>
[Creation of surface-treated steel sheet]
Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 50 g / L
Plating conditions Plating current density: 5 A / dm 2 ,
Plating bath temperature: 40 ° C
Tin plating amount: 2.8
[Production of resin-coated steel sheet]
Next, a transparent unstretched film having a thickness of 28 μm of ethylene terephthalate / ethylene isophthalate copolymer (PETI) is laminated on one side of the surface-treated steel sheet (the side that becomes the inner surface of the can), and the other side (can A white unstretched film having a thickness of 16 μm and containing 20% by mass of a titanium-based white pigment in an ethylene terephthalate / ethylene isophthalate copolymer (PETI) on the outer surface side) at a laminating temperature of 230 ° C. Lamination was performed, and immediately after the lamination of the resin film, the resin-coated steel sheet was prepared by cooling.
［表面処理鋼板の作成］
硫酸錫めっき組成
硫酸錫濃度（Ｓｎ濃度として）：５０ｇ／Ｌ
めっき条件
めっき電流密度：５Ａ／ｄｍ２、
めっき浴温度：４０℃、
錫めっき量：２．８
［樹脂被覆鋼板の作成］
次に、上記表面処理鋼板の片面（缶内面側になる面）に、エチレンテレフタレート・エチレンイソフタレート共重合体（ＰＥＴＩ）の厚さ２８μｍの透明無延伸フィルムを積層するとともに、他の片面（缶外面側になる面）に、エチレンテレフタレート・エチレンイソフタレート共重合体（ＰＥＴＩ）にチタン系白色顔料を２０質量％含有させた白色の厚さ１６μｍのホワイト無延伸フィルムを、ラミネート温度２３０℃にて積層し、樹脂フィルムの積層終了後は直ちに冷却して樹脂被覆鋼板を作成した。 <Example 1>
[Creation of surface-treated steel sheet]
Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 50 g / L
Plating conditions Plating current density: 5 A / dm 2 ,
Plating bath temperature: 40 ° C
Tin plating amount: 2.8
[Production of resin-coated steel sheet]
Next, a transparent unstretched film having a thickness of 28 μm of ethylene terephthalate / ethylene isophthalate copolymer (PETI) is laminated on one side of the surface-treated steel sheet (the side that becomes the inner surface of the can), and the other side (can A white unstretched film having a thickness of 16 μm and containing 20% by mass of a titanium-based white pigment in an ethylene terephthalate / ethylene isophthalate copolymer (PETI) on the outer surface side) at a laminating temperature of 230 ° C. Lamination was performed, and immediately after the lamination of the resin film, the resin-coated steel sheet was prepared by cooling.
＜実施例２＞
［表面処理鋼板の作成］
硫酸錫めっき組成
硫酸錫濃度（Ｓｎ濃度として）：７０ｇ／Ｌ
めっき条件
めっき電流密度：７Ａ／ｄｍ２、
めっき浴温度：４０℃、
錫めっき量：２．８
［樹脂被覆鋼板の作成］
実施例１と同様にして行った。 <Example 2>
[Creation of surface-treated steel sheet]
Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 70 g / L
Plating conditions Plating current density: 7 A / dm 2 ,
Plating bath temperature: 40 ° C
Tin plating amount: 2.8
[Production of resin-coated steel sheet]
The same operation as in Example 1 was performed.
［表面処理鋼板の作成］
硫酸錫めっき組成
硫酸錫濃度（Ｓｎ濃度として）：７０ｇ／Ｌ
めっき条件
めっき電流密度：７Ａ／ｄｍ２、
めっき浴温度：４０℃、
錫めっき量：２．８
［樹脂被覆鋼板の作成］
実施例１と同様にして行った。 <Example 2>
[Creation of surface-treated steel sheet]
Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 70 g / L
Plating conditions Plating current density: 7 A / dm 2 ,
Plating bath temperature: 40 ° C
Tin plating amount: 2.8
[Production of resin-coated steel sheet]
The same operation as in Example 1 was performed.
＜実施例３＞
［表面処理鋼板の作成］
硫酸錫めっき組成
硫酸錫濃度（Ｓｎ濃度として）：９０ｇ／Ｌ
めっき条件
めっき電流密度：１０Ａ／ｄｍ２、
めっき浴温度：４０℃、
錫めっき量：２．８
［樹脂被覆鋼板の作成］
実施例１と同様にして行った。 <Example 3>
[Creation of surface-treated steel sheet]
Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 90 g / L
Plating conditions Plating current density: 10 A / dm 2
Plating bath temperature: 40 ° C
Tin plating amount: 2.8
[Production of resin-coated steel sheet]
The same operation as in Example 1 was performed.
［表面処理鋼板の作成］
硫酸錫めっき組成
硫酸錫濃度（Ｓｎ濃度として）：９０ｇ／Ｌ
めっき条件
めっき電流密度：１０Ａ／ｄｍ２、
めっき浴温度：４０℃、
錫めっき量：２．８
［樹脂被覆鋼板の作成］
実施例１と同様にして行った。 <Example 3>
[Creation of surface-treated steel sheet]
Tin sulfate plating composition Tin sulfate concentration (as Sn concentration): 90 g / L
Plating conditions Plating current density: 10 A / dm 2
Plating bath temperature: 40 ° C
Tin plating amount: 2.8
[Production of resin-coated steel sheet]
The same operation as in Example 1 was performed.
＜評価＞
以下に、実施例１～３の表面処理鋼板の評価を述べる。
［表面観察］
図１（ａ）は、本発明の実施例１の鉄表面を露出した錫を鋼板表面に析出させた状態の表面処理鋼板の表面観察写真（ＳＥＭ像）であり、
図１（ｂ）は、比較例１の表面処理鋼板の表面観察写真である。
図１（ａ）に示すように、実施例１の表面処理鋼板においては、
平均粒子径１０μｍの鉄表面を露出した錫めっき層が、鉄素地が一部露出（地鉄露出）した鋼板上に鉄表面を露出した状態で分散析出していることが分かる。
一方、図１（ｂ）の比較例１の表面処理鋼板では、小さな金属錫粒子が鋼板上にべったりと析出しており、地鉄は露出していない。 <Evaluation>
Hereinafter, evaluation of the surface-treated steel sheets of Examples 1 to 3 will be described.
[Surface observation]
FIG. 1 (a) is a surface observation photograph (SEM image) of a surface-treated steel sheet in a state where tin exposed from the iron surface of Example 1 of the present invention is deposited on the steel sheet surface.
FIG. 1B is a surface observation photograph of the surface-treated steel sheet of Comparative Example 1.
As shown in FIG. 1 (a), in the surface-treated steel sheet of Example 1,
It can be seen that the tin plating layer exposing the iron surface having an average particle diameter of 10 μm is dispersed and precipitated in a state where the iron surface is exposed on the steel sheet where the iron base is partially exposed (exposed to the iron base).
On the other hand, in the surface-treated steel sheet of Comparative Example 1 in FIG. 1B, small metal tin particles are deposited on the steel sheet, and the ground iron is not exposed.
以下に、実施例１～３の表面処理鋼板の評価を述べる。
［表面観察］
図１（ａ）は、本発明の実施例１の鉄表面を露出した錫を鋼板表面に析出させた状態の表面処理鋼板の表面観察写真（ＳＥＭ像）であり、
図１（ｂ）は、比較例１の表面処理鋼板の表面観察写真である。
図１（ａ）に示すように、実施例１の表面処理鋼板においては、
平均粒子径１０μｍの鉄表面を露出した錫めっき層が、鉄素地が一部露出（地鉄露出）した鋼板上に鉄表面を露出した状態で分散析出していることが分かる。
一方、図１（ｂ）の比較例１の表面処理鋼板では、小さな金属錫粒子が鋼板上にべったりと析出しており、地鉄は露出していない。 <Evaluation>
Hereinafter, evaluation of the surface-treated steel sheets of Examples 1 to 3 will be described.
[Surface observation]
FIG. 1 (a) is a surface observation photograph (SEM image) of a surface-treated steel sheet in a state where tin exposed from the iron surface of Example 1 of the present invention is deposited on the steel sheet surface.
FIG. 1B is a surface observation photograph of the surface-treated steel sheet of Comparative Example 1.
As shown in FIG. 1 (a), in the surface-treated steel sheet of Example 1,
It can be seen that the tin plating layer exposing the iron surface having an average particle diameter of 10 μm is dispersed and precipitated in a state where the iron surface is exposed on the steel sheet where the iron base is partially exposed (exposed to the iron base).
On the other hand, in the surface-treated steel sheet of Comparative Example 1 in FIG. 1B, small metal tin particles are deposited on the steel sheet, and the ground iron is not exposed.
＜密着性評価＞
［１ｓｔカップの製造］
次に、本発明及び比較例の表面処理鋼板に樹脂フィルムを積層した樹脂被覆鋼板を、
直径：１５１ｍｍのブランクに打ち抜いた後、透明無延伸フィルム被覆面がカップ内面側となるようにして（ホワイト無延伸フィルムを被覆した面が缶の外面となる）、絞り比：１．６４の１段絞り加工を施して絞り、１ｓｔカップ、Ｂ／Ｍ缶、ＣＨＳ缶を作成し、透明無延伸フィルム被覆面が測定面となるようにして、密着性評価用の試片を作成した。
これらの試片を引張試験機にかけてＳピール強度を測定した。
また、１ｓｔカップ、Ｂ／Ｍ缶、ＣＨＳ缶のカップ先端デラミ（フィルム剥離）の有無を観察した。
さらに、樹脂被覆鋼板自体についても、Ｓピール強度を測定するとともに、ラミネート後の外観を目視で確認した（デラミ観察）。
なお、ここで、１ｓｔカップは板を絞り加工して製造したものをいい、Ｂ／Ｍ缶は１ｓｔカップをさらに絞り、しごき加工して缶径が小さく側壁高さの高い缶に成形したものをいい、ＣＨＳ缶はＢ／Ｍ缶をさらにトリム、フランジ、ネック加工して製造したものをいう。
上記評価結果を表１～６の密着性評価の欄に示す。 <Adhesion evaluation>
[Production of 1st cup]
Next, a resin-coated steel sheet obtained by laminating a resin film on the surface-treated steel sheet of the present invention and the comparative example,
After punching into a blank having a diameter of 151 mm, the transparent unstretched film-coated surface is the inner surface of the cup (the surface coated with the white unstretched film is the outer surface of the can), and the drawing ratio is 1.64. A step-drawing process was performed to prepare a first cup, a B / M can, and a CHS can, and a test piece for adhesion evaluation was prepared so that the transparent unstretched film-coated surface became the measurement surface.
These specimens were subjected to a tensile tester to measure S peel strength.
Further, the presence or absence of delamination (film peeling) of the 1st cup, B / M can, and CHS can was observed.
Further, the S-peel strength was also measured for the resin-coated steel sheet itself, and the appearance after lamination was visually confirmed (delamination observation).
In addition, 1st cup means what was manufactured by squeezing a board, and B / M can is a thing formed by further squeezing and squeezing the 1st cup to form a can with a small can diameter and a high side wall height. Okay, CHS cans are manufactured by trimming, flange, and necking B / M cans.
The evaluation results are shown in the column of adhesion evaluation in Tables 1-6.
［１ｓｔカップの製造］
次に、本発明及び比較例の表面処理鋼板に樹脂フィルムを積層した樹脂被覆鋼板を、
直径：１５１ｍｍのブランクに打ち抜いた後、透明無延伸フィルム被覆面がカップ内面側となるようにして（ホワイト無延伸フィルムを被覆した面が缶の外面となる）、絞り比：１．６４の１段絞り加工を施して絞り、１ｓｔカップ、Ｂ／Ｍ缶、ＣＨＳ缶を作成し、透明無延伸フィルム被覆面が測定面となるようにして、密着性評価用の試片を作成した。
これらの試片を引張試験機にかけてＳピール強度を測定した。
また、１ｓｔカップ、Ｂ／Ｍ缶、ＣＨＳ缶のカップ先端デラミ（フィルム剥離）の有無を観察した。
さらに、樹脂被覆鋼板自体についても、Ｓピール強度を測定するとともに、ラミネート後の外観を目視で確認した（デラミ観察）。
なお、ここで、１ｓｔカップは板を絞り加工して製造したものをいい、Ｂ／Ｍ缶は１ｓｔカップをさらに絞り、しごき加工して缶径が小さく側壁高さの高い缶に成形したものをいい、ＣＨＳ缶はＢ／Ｍ缶をさらにトリム、フランジ、ネック加工して製造したものをいう。
上記評価結果を表１～６の密着性評価の欄に示す。 <Adhesion evaluation>
[Production of 1st cup]
Next, a resin-coated steel sheet obtained by laminating a resin film on the surface-treated steel sheet of the present invention and the comparative example,
After punching into a blank having a diameter of 151 mm, the transparent unstretched film-coated surface is the inner surface of the cup (the surface coated with the white unstretched film is the outer surface of the can), and the drawing ratio is 1.64. A step-drawing process was performed to prepare a first cup, a B / M can, and a CHS can, and a test piece for adhesion evaluation was prepared so that the transparent unstretched film-coated surface became the measurement surface.
These specimens were subjected to a tensile tester to measure S peel strength.
Further, the presence or absence of delamination (film peeling) of the 1st cup, B / M can, and CHS can was observed.
Further, the S-peel strength was also measured for the resin-coated steel sheet itself, and the appearance after lamination was visually confirmed (delamination observation).
In addition, 1st cup means what was manufactured by squeezing a board, and B / M can is a thing formed by further squeezing and squeezing the 1st cup to form a can with a small can diameter and a high side wall height. Okay, CHS cans are manufactured by trimming, flange, and necking B / M cans.
The evaluation results are shown in the column of adhesion evaluation in Tables 1-6.
実施例１～３の表面処理鋼板から作成した樹脂被覆鋼板を用いたカップは、１ｓｔカップにおいて、Ｓピール強度は、１ｓｔカップで、それぞれ０．２５ｇ／１５ｍｍ、０．３５ｇ／１５ｍｍ、０．５ｇ／１５ｍｍ以上の値を示し、缶成形加工時の際の樹脂フィルムの加工密着性に優れていた。
さらに、１ｓｔカップ、Ｂ／Ｍ缶及びＣＨＳ缶のカップ先端デラミは観察されなかった（○印）。
これに対し、比較例の表面処理鋼板から作成した樹脂被覆鋼板を用いたものは、１ｓｔカップに成形加工を行った際に、カップ先端部の樹脂フィルムと表面処理鋼板とが密着性不良となり、カップ先端部にデラミが発生した。 The cups using the resin-coated steel plates prepared from the surface-treated steel plates of Examples 1 to 3 are 1st cups, and the S peel strength is 0.25 g / 15 mm, 0.35 g / 15 mm, and 0.5 g, respectively. / 15 mm or more, showing excellent process adhesion of the resin film during can molding.
Further, no delamination of the cup tip of the 1st cup, B / M can and CHS can was observed (circle mark).
On the other hand, when using the resin-coated steel sheet prepared from the surface-treated steel sheet of the comparative example, when forming the 1st cup, the resin film at the tip of the cup and the surface-treated steel sheet become poor adhesion, Delamination occurred at the tip of the cup.
さらに、１ｓｔカップ、Ｂ／Ｍ缶及びＣＨＳ缶のカップ先端デラミは観察されなかった（○印）。
これに対し、比較例の表面処理鋼板から作成した樹脂被覆鋼板を用いたものは、１ｓｔカップに成形加工を行った際に、カップ先端部の樹脂フィルムと表面処理鋼板とが密着性不良となり、カップ先端部にデラミが発生した。 The cups using the resin-coated steel plates prepared from the surface-treated steel plates of Examples 1 to 3 are 1st cups, and the S peel strength is 0.25 g / 15 mm, 0.35 g / 15 mm, and 0.5 g, respectively. / 15 mm or more, showing excellent process adhesion of the resin film during can molding.
Further, no delamination of the cup tip of the 1st cup, B / M can and CHS can was observed (circle mark).
On the other hand, when using the resin-coated steel sheet prepared from the surface-treated steel sheet of the comparative example, when forming the 1st cup, the resin film at the tip of the cup and the surface-treated steel sheet become poor adhesion, Delamination occurred at the tip of the cup.
本発明において、密着性向上の要因は、以下のように考えられる。
すなわち、１ｓｔカップの状態での密着性評価として、
例えば、実施例１（表２参照）と比較例１（表１参照）とで比較すると、錫めっき量（Ｓｎ＝２．８ｇ／ｍ２）、被覆時の表面処理鋼板加熱温度（ラミネート温度＝２３０℃）は同じであるが、１ｓｔカップのＳピール強度は、それぞれ０．２５ｋｇ／１５ｍｍ、０．０５ｋｇ／１５ｍｍであり、５０倍の有意差が有る。 In the present invention, the factors for improving the adhesion are considered as follows.
That is, as an adhesion evaluation in the state of the 1st cup,
For example, when compared between Example 1 (see Table 2) and Comparative Example 1 (see Table 1), the tin plating amount (Sn = 2.8 g / m 2 ), the surface-treated steel sheet heating temperature during coating (laminate temperature = 230 ° C.), but the S peel strength of the 1st cup is 0.25 kg / 15 mm and 0.05 kg / 15 mm, respectively, and there is a 50-fold significant difference.
すなわち、１ｓｔカップの状態での密着性評価として、
例えば、実施例１（表２参照）と比較例１（表１参照）とで比較すると、錫めっき量（Ｓｎ＝２．８ｇ／ｍ２）、被覆時の表面処理鋼板加熱温度（ラミネート温度＝２３０℃）は同じであるが、１ｓｔカップのＳピール強度は、それぞれ０．２５ｋｇ／１５ｍｍ、０．０５ｋｇ／１５ｍｍであり、５０倍の有意差が有る。 In the present invention, the factors for improving the adhesion are considered as follows.
That is, as an adhesion evaluation in the state of the 1st cup,
For example, when compared between Example 1 (see Table 2) and Comparative Example 1 (see Table 1), the tin plating amount (Sn = 2.8 g / m 2 ), the surface-treated steel sheet heating temperature during coating (laminate temperature = 230 ° C.), but the S peel strength of the 1st cup is 0.25 kg / 15 mm and 0.05 kg / 15 mm, respectively, and there is a 50-fold significant difference.
また、対応する図１（ａ）（実施例１）と図１（ｂ）（比較例１）の錫めっき後の表面処理鋼板の外観を比較すると、錫の電着形態に差が有り、実施例１の鉄表面を露出した錫を形成した表面処理鋼板は、表層錫面積率が８８％、平均錫粒子サイズが５μｍで、錫粒子が大きく凹凸の多い表面となっているのに対し、
比較例１の従来製造法の表面処理鋼板は、表層錫面積率が９８％、平均錫粒子サイズが０．３μｍで、凹凸の少ない表面となっていることが分かる。同様のことは、その他の実施例、比較例についても言えることである。 Moreover, when the appearance of the surface-treated steel sheet after tin plating in FIG. 1 (a) (Example 1) and FIG. 1 (b) (Comparative Example 1) is compared, there is a difference in tin electrodeposition. In the surface-treated steel sheet formed with tin with the iron surface exposed in Example 1, the surface layer tin area ratio is 88%, the average tin particle size is 5 μm, and the tin particle has a large and uneven surface,
It can be seen that the surface-treated steel sheet according to the conventional manufacturing method of Comparative Example 1 has a surface tin area ratio of 98%, an average tin particle size of 0.3 μm, and a surface with little unevenness. The same applies to the other examples and comparative examples.
比較例１の従来製造法の表面処理鋼板は、表層錫面積率が９８％、平均錫粒子サイズが０．３μｍで、凹凸の少ない表面となっていることが分かる。同様のことは、その他の実施例、比較例についても言えることである。 Moreover, when the appearance of the surface-treated steel sheet after tin plating in FIG. 1 (a) (Example 1) and FIG. 1 (b) (Comparative Example 1) is compared, there is a difference in tin electrodeposition. In the surface-treated steel sheet formed with tin with the iron surface exposed in Example 1, the surface layer tin area ratio is 88%, the average tin particle size is 5 μm, and the tin particle has a large and uneven surface,
It can be seen that the surface-treated steel sheet according to the conventional manufacturing method of Comparative Example 1 has a surface tin area ratio of 98%, an average tin particle size of 0.3 μm, and a surface with little unevenness. The same applies to the other examples and comparative examples.
また、実施例１と比較例１とにおいて樹脂フィルムの密着性（Ｓピール強度）に大きく差が見られる１ｓｔカップの缶壁（Ｓピール強度試験後の表面処理鋼板表面）を観察すると、鉄表面を露出した錫めっきを施した表面処理鋼板表面は、めっき凹部（錫の電着が無く、鉄表面が露出している部分）に接着していた樹脂フィルムの跡がシュリンク状になっていることが観察された。
Moreover, when the 1st cup can wall (surface-treated steel plate surface after S peel strength test) in which the difference in the adhesiveness (S peel strength) of the resin film is significantly different between Example 1 and Comparative Example 1 is observed, the iron surface The surface of the surface-treated steel sheet with tin plating exposed is shrunk on the surface of the resin film adhering to the plating recess (the part where there is no tin electrodeposition and the iron surface is exposed). Was observed.
なお、表１～表６に示す実施例及び比較例において、
めっき外観の表示が「地鉄露出」と記載してあり、かつ本発明の範囲内の条件のものは、錫面積率が９０％以下、Ｓピール強度が０．２ｋｇ／１５ｍｍ以上であった。
本発明の範囲外の条件で表面処理を行ったものについては、
めっき外観を「地鉄露出」、「全面被覆」、「デンドライト析出」、「デンドライト」と表記した。以下に比較例の説明をする。
めっき外観の表示が「地鉄露出」と記載してあるが本発明の範囲外の条件のものは、錫面積率が９８％、Ｓピール強度が０．０５ｋｇ／１５ｍｍであった（比較例－１）。
めっき外観の表示が「全面被覆」と記載してあるが本発明の範囲外の条件のものは、錫面積率が１００％、Ｓピール強度が０．０２ｋｇ／１５ｍｍであった。
めっき外観の表示が「デンドライト析出」又は「デンドライト」（樹枝状析出）と記載してあるが本発明の範囲外の条件のものは、適正電流密度範囲を超えためっき状態で、めっき表面に金属Ｓｎ粉体が析出して黒い色調を呈しており商品価値が無いものである。錫面積率は１００％、Ｓピール強度は０．０１ｋｇ／１５ｍｍであった。
なお、表中、上方向の矢印（↑）の表記は、その上の欄に記載のものと同じ状態であることを意味する。 In Examples and Comparative Examples shown in Tables 1 to 6,
The display of the appearance of the plating is described as “exposed steel”, and the conditions within the scope of the present invention were a tin area ratio of 90% or less and an S peel strength of 0.2 kg / 15 mm or more.
For those subjected to surface treatment under conditions outside the scope of the present invention,
The appearance of the plating was expressed as “base metal exposure”, “entire coverage”, “dendritic precipitation”, and “dendritic”. A comparative example will be described below.
Although the display of the plating appearance is described as “exposed steel”, the tin area ratio was 98% and the S peel strength was 0.05 kg / 15 mm under the conditions outside the scope of the present invention (Comparative Example— 1).
Although the display of the plating appearance is described as “overall coating”, the condition outside the scope of the present invention was that the tin area ratio was 100% and the S peel strength was 0.02 kg / 15 mm.
The indication of plating appearance is described as “dendritic precipitation” or “dendritic” (dendritic precipitation), but the conditions outside the scope of the present invention are in the plating state exceeding the appropriate current density range, and the metal is plated on the plating surface. The Sn powder is precipitated and has a black color tone, which has no commercial value. The tin area ratio was 100%, and the S peel strength was 0.01 kg / 15 mm.
In the table, the notation of the upward arrow (↑) means the same state as that described in the column above it.
めっき外観の表示が「地鉄露出」と記載してあり、かつ本発明の範囲内の条件のものは、錫面積率が９０％以下、Ｓピール強度が０．２ｋｇ／１５ｍｍ以上であった。
本発明の範囲外の条件で表面処理を行ったものについては、
めっき外観を「地鉄露出」、「全面被覆」、「デンドライト析出」、「デンドライト」と表記した。以下に比較例の説明をする。
めっき外観の表示が「地鉄露出」と記載してあるが本発明の範囲外の条件のものは、錫面積率が９８％、Ｓピール強度が０．０５ｋｇ／１５ｍｍであった（比較例－１）。
めっき外観の表示が「全面被覆」と記載してあるが本発明の範囲外の条件のものは、錫面積率が１００％、Ｓピール強度が０．０２ｋｇ／１５ｍｍであった。
めっき外観の表示が「デンドライト析出」又は「デンドライト」（樹枝状析出）と記載してあるが本発明の範囲外の条件のものは、適正電流密度範囲を超えためっき状態で、めっき表面に金属Ｓｎ粉体が析出して黒い色調を呈しており商品価値が無いものである。錫面積率は１００％、Ｓピール強度は０．０１ｋｇ／１５ｍｍであった。
なお、表中、上方向の矢印（↑）の表記は、その上の欄に記載のものと同じ状態であることを意味する。 In Examples and Comparative Examples shown in Tables 1 to 6,
The display of the appearance of the plating is described as “exposed steel”, and the conditions within the scope of the present invention were a tin area ratio of 90% or less and an S peel strength of 0.2 kg / 15 mm or more.
For those subjected to surface treatment under conditions outside the scope of the present invention,
The appearance of the plating was expressed as “base metal exposure”, “entire coverage”, “dendritic precipitation”, and “dendritic”. A comparative example will be described below.
Although the display of the plating appearance is described as “exposed steel”, the tin area ratio was 98% and the S peel strength was 0.05 kg / 15 mm under the conditions outside the scope of the present invention (Comparative Example— 1).
Although the display of the plating appearance is described as “overall coating”, the condition outside the scope of the present invention was that the tin area ratio was 100% and the S peel strength was 0.02 kg / 15 mm.
The indication of plating appearance is described as “dendritic precipitation” or “dendritic” (dendritic precipitation), but the conditions outside the scope of the present invention are in the plating state exceeding the appropriate current density range, and the metal is plated on the plating surface. The Sn powder is precipitated and has a black color tone, which has no commercial value. The tin area ratio was 100%, and the S peel strength was 0.01 kg / 15 mm.
In the table, the notation of the upward arrow (↑) means the same state as that described in the column above it.
＜製缶後の耐食性評価＞
耐食性評価は、製缶後の缶側壁部を切り出し、クロスカット（カッタ－ナイフで２０ｍｍ×２０ｍｍの切り込みを入れる）部の腐食性を比較した。
試験要領を以下に記述する。
（１）樹脂被覆処理
当該表面処理鋼板の缶外面になる面には、厚さ１６μｍの、Ｔｉ顔料を２０％程度含有するポリエチレンテレフタレート／イソフタレート（１２モル％）のＰＥＴフィルムを、また、缶内面になる面には、厚さ２８μｍの、Ｔｉ顔料を含まないポリエチレンテレフタレート／イソフタレート（１２モル％）のＰＥＴフィルムを、ラミネートロールを介して熱圧着し樹脂被覆鋼板とした。
（２）製缶工程
当該樹脂被覆鋼板から、直径１５４ｍｍのブランクを打ち抜き、絞り比＝１．６４で第１段の絞り加工を施し、直径９６ｍｍ，高さ４２ｍｍの絞りカップ（１ｓｔカップ）を成形した。このカップを更に再絞り、しごき加工し、直径５２ｍｍ，高さ１３８ｍｍの絞りしごきカップ（２ｎｄカップ）を成形した。
更に、樹脂フィルムの歪を取り除くため、２２０℃で約１分間保持する熱処理を行い、最終成形缶（Ｆｉ缶）とした。
（３）腐食試験片作製
最終成形缶の缶壁を４０ｍｍ×４０ｍｍの正方形に切り出し、缶内面側の中央部より十字クロスカット（２０ｍｍ×２０ｍｍの切り込み）をカッタ－ナイフで入れ、内径３５ｍｍ、高さ４０ｍｍ、外径３８ｍｍの円筒状ガラスセルをクロスカット面上に設置し、セルの上下を８０ｍｍ×８０ｍｍ、厚さ５ｍｍの塩ビ板で固定した（４隅をボルト締め）。
（４）腐食液の注入
腐食試験液を１００ｍＬ注入し、密封後、恒温室３７℃で１週間経時した。
（５）耐食性評価
恒温室からセルを取り出し、腐食液中に溶出している鉄および錫量を原子吸光装置で測定し、更にクロスカット部の腐食状態（腐食巾）を比較した。
<Evaluation of corrosion resistance after canning>
In the corrosion resistance evaluation, the side wall of the can after cutting was cut out, and the corrosiveness of the cross cut (20 mm × 20 mm cut with a cutter knife) was compared.
The test procedure is described below.
(1) Resin coating treatment A PET film of polyethylene terephthalate / isophthalate (12 mol%) having a thickness of 16 μm and containing about 20% of a Ti pigment is also formed on the surface of the surface-treated steel sheet. On the inner surface, a PET film of polyethylene terephthalate / isophthalate (12 mol%) having a thickness of 28 μm and containing no Ti pigment was thermocompression bonded through a laminate roll to obtain a resin-coated steel sheet.
(2) Can-making process A blank with a diameter of 154 mm is punched from the resin-coated steel sheet, the first stage drawing is performed with a drawing ratio = 1.64, and a drawn cup (1 st cup) with a diameter of 96 mm and a height of 42 mm is obtained. Molded. The cup further redrawn to, and ironing, was molded cup (2 nd cup) ironing aperture diameter 52 mm, height 138 mm.
Furthermore, in order to remove the distortion of the resin film, a heat treatment was carried out at 220 ° C. for about 1 minute to obtain a final molded can (Fi can).
(3) Corrosion test piece production The can wall of the final molded can was cut into a 40 mm x 40 mm square, and a cross cross cut (20 mm x 20 mm cut) was made with a cutter knife from the center of the inner surface of the can. A cylindrical glass cell having a thickness of 40 mm and an outer diameter of 38 mm was placed on the crosscut surface, and the top and bottom of the cell were fixed with a vinyl chloride plate having a thickness of 80 mm × 80 mm and a thickness of 5 mm (four corners were bolted).
(4) Injection of corrosive liquid 100 mL of the corrosive test liquid was injected, sealed, and then aged for one week at 37 ° C. in a thermostatic chamber.
(5) Evaluation of corrosion resistance The cell was taken out from the temperature-controlled room, the amount of iron and tin eluted in the corrosive liquid was measured with an atomic absorption device, and the corrosion state (corrosion width) of the cross-cut portion was compared.
耐食性評価は、製缶後の缶側壁部を切り出し、クロスカット（カッタ－ナイフで２０ｍｍ×２０ｍｍの切り込みを入れる）部の腐食性を比較した。
試験要領を以下に記述する。
（１）樹脂被覆処理
当該表面処理鋼板の缶外面になる面には、厚さ１６μｍの、Ｔｉ顔料を２０％程度含有するポリエチレンテレフタレート／イソフタレート（１２モル％）のＰＥＴフィルムを、また、缶内面になる面には、厚さ２８μｍの、Ｔｉ顔料を含まないポリエチレンテレフタレート／イソフタレート（１２モル％）のＰＥＴフィルムを、ラミネートロールを介して熱圧着し樹脂被覆鋼板とした。
（２）製缶工程
当該樹脂被覆鋼板から、直径１５４ｍｍのブランクを打ち抜き、絞り比＝１．６４で第１段の絞り加工を施し、直径９６ｍｍ，高さ４２ｍｍの絞りカップ（１ｓｔカップ）を成形した。このカップを更に再絞り、しごき加工し、直径５２ｍｍ，高さ１３８ｍｍの絞りしごきカップ（２ｎｄカップ）を成形した。
更に、樹脂フィルムの歪を取り除くため、２２０℃で約１分間保持する熱処理を行い、最終成形缶（Ｆｉ缶）とした。
（３）腐食試験片作製
最終成形缶の缶壁を４０ｍｍ×４０ｍｍの正方形に切り出し、缶内面側の中央部より十字クロスカット（２０ｍｍ×２０ｍｍの切り込み）をカッタ－ナイフで入れ、内径３５ｍｍ、高さ４０ｍｍ、外径３８ｍｍの円筒状ガラスセルをクロスカット面上に設置し、セルの上下を８０ｍｍ×８０ｍｍ、厚さ５ｍｍの塩ビ板で固定した（４隅をボルト締め）。
（４）腐食液の注入
腐食試験液を１００ｍＬ注入し、密封後、恒温室３７℃で１週間経時した。
（５）耐食性評価
恒温室からセルを取り出し、腐食液中に溶出している鉄および錫量を原子吸光装置で測定し、更にクロスカット部の腐食状態（腐食巾）を比較した。
In the corrosion resistance evaluation, the side wall of the can after cutting was cut out, and the corrosiveness of the cross cut (20 mm × 20 mm cut with a cutter knife) was compared.
The test procedure is described below.
(1) Resin coating treatment A PET film of polyethylene terephthalate / isophthalate (12 mol%) having a thickness of 16 μm and containing about 20% of a Ti pigment is also formed on the surface of the surface-treated steel sheet. On the inner surface, a PET film of polyethylene terephthalate / isophthalate (12 mol%) having a thickness of 28 μm and containing no Ti pigment was thermocompression bonded through a laminate roll to obtain a resin-coated steel sheet.
(2) Can-making process A blank with a diameter of 154 mm is punched from the resin-coated steel sheet, the first stage drawing is performed with a drawing ratio = 1.64, and a drawn cup (1 st cup) with a diameter of 96 mm and a height of 42 mm is obtained. Molded. The cup further redrawn to, and ironing, was molded cup (2 nd cup) ironing aperture diameter 52 mm, height 138 mm.
Furthermore, in order to remove the distortion of the resin film, a heat treatment was carried out at 220 ° C. for about 1 minute to obtain a final molded can (Fi can).
(3) Corrosion test piece production The can wall of the final molded can was cut into a 40 mm x 40 mm square, and a cross cross cut (20 mm x 20 mm cut) was made with a cutter knife from the center of the inner surface of the can. A cylindrical glass cell having a thickness of 40 mm and an outer diameter of 38 mm was placed on the crosscut surface, and the top and bottom of the cell were fixed with a vinyl chloride plate having a thickness of 80 mm × 80 mm and a thickness of 5 mm (four corners were bolted).
(4) Injection of corrosive liquid 100 mL of the corrosive test liquid was injected, sealed, and then aged for one week at 37 ° C. in a thermostatic chamber.
(5) Evaluation of corrosion resistance The cell was taken out from the temperature-controlled room, the amount of iron and tin eluted in the corrosive liquid was measured with an atomic absorption device, and the corrosion state (corrosion width) of the cross-cut portion was compared.
以上説明したように、本発明の製造方法によって製造された表面処理鋼板を用いた樹脂被覆鋼板は、絞り加工、絞り加工後のさらなるストレッチ加工、絞り加工後のさらなるしごき加工、のいずれの加工を施しても、成形加工時において樹脂フィルムが剥離することなく、安定した、また、より過酷な絞り加工後にさらにストレッチ加工としごき加工を併用する加工を施す缶体成形加工時においても、樹脂フィルムが剥離することがなく、安定して優れた加工密着性を示す。
As described above, the resin-coated steel sheet using the surface-treated steel sheet manufactured by the manufacturing method of the present invention is subjected to any one of drawing, further stretching after drawing, and further ironing after drawing. Even if it is applied, the resin film does not peel off during the molding process, and the resin film is stable even during the can body molding process, which is subjected to a process that is combined with a stretch process and an ironing process after a more severe drawing process. It does not peel off and shows excellent processing adhesion stably.
なお、従来、被覆樹脂の密着性の評価法として、加工前の平板の状態でＴピール強度を測定していたが、加工密着性を必ずしも正確に反映していないと考えられるので、本発明においては、剥離強度としてのＳピール強度を採用した。すなわち、絞り加工後さらにストレッチ加工としごき加工を併用して加工して缶体に成形するような厳しい成形加工を施した場合の、加工中および加工後の密着性（加工密着性）を正確に反映する評価法としてＳピール強度を採用した。
Ｓピール強度とは、樹脂被覆鋼板を絞り加工を施してカップに成形加工し、カップ側壁から試片を切り出し、その試片の樹脂膜の剥離強度で加工密着強度を評価するものである。 Conventionally, as a method for evaluating the adhesion of the coating resin, the T peel strength was measured in the state of a flat plate before processing, but it is considered that the processing adhesion is not necessarily accurately reflected. Adopted S peel strength as peel strength. In other words, the adhesiveness (working adhesion) during and after processing is accurate when strict forming processing is performed, such as drawing and drawing together with the ironing process after drawing. S peel strength was adopted as an evaluation method to be reflected.
The S peel strength is formed by drawing a resin-coated steel sheet into a cup, cutting a specimen from the side wall of the cup, and evaluating the work adhesion strength by the peel strength of the resin film of the specimen.
Ｓピール強度とは、樹脂被覆鋼板を絞り加工を施してカップに成形加工し、カップ側壁から試片を切り出し、その試片の樹脂膜の剥離強度で加工密着強度を評価するものである。 Conventionally, as a method for evaluating the adhesion of the coating resin, the T peel strength was measured in the state of a flat plate before processing, but it is considered that the processing adhesion is not necessarily accurately reflected. Adopted S peel strength as peel strength. In other words, the adhesiveness (working adhesion) during and after processing is accurate when strict forming processing is performed, such as drawing and drawing together with the ironing process after drawing. S peel strength was adopted as an evaluation method to be reflected.
The S peel strength is formed by drawing a resin-coated steel sheet into a cup, cutting a specimen from the side wall of the cup, and evaluating the work adhesion strength by the peel strength of the resin film of the specimen.
Ｓピール強度の具体的な測定方法を以下に示す。
まず、樹脂被覆鋼板から、直径１５４ｍｍのブランクを打ち抜き、絞り比：１．６４で第一段の絞り加工を施して、径：９６ｍｍ、高さ：４２ｍｍの絞りカップを成形する。このカップから、カップ高さ方向：３０ｍｍ、カップ周方向：１２０ｍｍの大きさで絞りカップの側壁部を切り出して平板状に曲げ戻した後、図２の平面図に示すようなサイズのＴ字形状の試片７１をプレス金型を用いて打ち抜く。
次いで、図３に示すように、カッターナイフを用いて試片７１の一方（右）の端部７１ａの密着強度測定面（図示では手前の面）と反対の側の被覆樹脂（図示では裏側の面）に、表面処理鋼板面に達するように切れ目７２を入れる。
さらに、図４および図５に示すように、スコア加工用ダイセットを用いて、密着強度測定面と反対の側（切れ目７２を入れた面）にスコア７３を入れた後、スコア部を折り曲げて表面処理鋼板のみを切断する。この時、密着強度測定面においては、被覆樹脂は切断されることなく、切断分離された表面処理鋼板の両側に繋がったまま残っている。
次いで、図６に示すように、試片ホルダー７４の試片挿入部７４ａに片端部７１ａを挿入して、試片７１を試片ホルダー７４に固定した後、試片ホルダー７４の上部７４ｂと試片７１の他方の端部７１ｂとを、引張試験機の両チャック部で挟んで引張り、被覆樹脂を表面処理鋼板から強制剥離して引張強度を測定し、この値をＳピール強度とした。 A specific method for measuring the S peel strength is shown below.
First, a blank having a diameter of 154 mm is punched out of a resin-coated steel sheet, and a first-stage drawing is performed at a drawing ratio of 1.64 to form a drawn cup having a diameter of 96 mm and a height of 42 mm. From this cup, after cutting out the side wall portion of the squeeze cup in a cup height direction: 30 mm and a cup circumferential direction: 120 mm and bending it back into a flat plate shape, a T-shape having a size as shown in the plan view of FIG. Thetest piece 71 is punched out using a press die.
Next, as shown in FIG. 3, using a cutter knife, a coating resin (on the back side in the drawing) on the side opposite to the adhesion strength measuring surface (the front side in the drawing) of one (right)end 71a of the specimen 71 is used. The cut 72 is made so as to reach the surface-treated steel sheet surface.
Further, as shown in FIG. 4 and FIG. 5, using the score processing die set, after putting thescore 73 on the side opposite to the adhesion strength measuring surface (the surface with the cut 72), the score portion is bent. Only the surface-treated steel sheet is cut. At this time, on the adhesion strength measurement surface, the coating resin remains connected to both sides of the cut and separated surface-treated steel sheet without being cut.
Next, as shown in FIG. 6, after inserting oneend 71 a into the specimen insertion portion 74 a of the specimen holder 74 and fixing the specimen 71 to the specimen holder 74, the upper part 74 b of the specimen holder 74 and the specimen 74 are arranged. The other end portion 71b of the piece 71 was sandwiched between the two chuck portions of the tensile tester, and the tensile strength was measured by forcibly peeling the coating resin from the surface-treated steel sheet, and this value was defined as the S peel strength.
まず、樹脂被覆鋼板から、直径１５４ｍｍのブランクを打ち抜き、絞り比：１．６４で第一段の絞り加工を施して、径：９６ｍｍ、高さ：４２ｍｍの絞りカップを成形する。このカップから、カップ高さ方向：３０ｍｍ、カップ周方向：１２０ｍｍの大きさで絞りカップの側壁部を切り出して平板状に曲げ戻した後、図２の平面図に示すようなサイズのＴ字形状の試片７１をプレス金型を用いて打ち抜く。
次いで、図３に示すように、カッターナイフを用いて試片７１の一方（右）の端部７１ａの密着強度測定面（図示では手前の面）と反対の側の被覆樹脂（図示では裏側の面）に、表面処理鋼板面に達するように切れ目７２を入れる。
さらに、図４および図５に示すように、スコア加工用ダイセットを用いて、密着強度測定面と反対の側（切れ目７２を入れた面）にスコア７３を入れた後、スコア部を折り曲げて表面処理鋼板のみを切断する。この時、密着強度測定面においては、被覆樹脂は切断されることなく、切断分離された表面処理鋼板の両側に繋がったまま残っている。
次いで、図６に示すように、試片ホルダー７４の試片挿入部７４ａに片端部７１ａを挿入して、試片７１を試片ホルダー７４に固定した後、試片ホルダー７４の上部７４ｂと試片７１の他方の端部７１ｂとを、引張試験機の両チャック部で挟んで引張り、被覆樹脂を表面処理鋼板から強制剥離して引張強度を測定し、この値をＳピール強度とした。 A specific method for measuring the S peel strength is shown below.
First, a blank having a diameter of 154 mm is punched out of a resin-coated steel sheet, and a first-stage drawing is performed at a drawing ratio of 1.64 to form a drawn cup having a diameter of 96 mm and a height of 42 mm. From this cup, after cutting out the side wall portion of the squeeze cup in a cup height direction: 30 mm and a cup circumferential direction: 120 mm and bending it back into a flat plate shape, a T-shape having a size as shown in the plan view of FIG. The
Next, as shown in FIG. 3, using a cutter knife, a coating resin (on the back side in the drawing) on the side opposite to the adhesion strength measuring surface (the front side in the drawing) of one (right)
Further, as shown in FIG. 4 and FIG. 5, using the score processing die set, after putting the
Next, as shown in FIG. 6, after inserting one
上記のようにして測定されるＳピール強度は、試片の巾１５ｍｍにおいて、０．２ｋｇ／１５ｍｍ以上であることが好ましい。Ｓピール強度が０．２ｋｇ／１５ｍｍ未満であると、絞り加工後さらにストレッチ加工としごき加工を併用した製缶加工などの厳しい成形加工において安定した良好な加工密着性が得られない。
The S peel strength measured as described above is preferably 0.2 kg / 15 mm or more when the width of the specimen is 15 mm. If the S peel strength is less than 0.2 kg / 15 mm, stable and good working adhesion cannot be obtained in severe molding processes such as a can-making process using a stretch process and an ironing process after drawing.
本発明は、従来の表面処理鋼板の欠点である樹脂との密着性を向上させることによって、樹脂被覆鋼板の加工性を低下させずに耐腐食性を向上させた表面処理鋼板を、安定して製造することができ、工業的な価値は極めて大である。
The present invention stably improves the surface-treated steel sheet with improved corrosion resistance without reducing the workability of the resin-coated steel sheet by improving the adhesion with the resin, which is a drawback of the conventional surface-treated steel sheet. It can be manufactured and has industrial value.
７１：試片
７１ａ：試片の一方の端部
７１ｂ：試片の他方の端部
７２：切れ目
７３：スコア
７４：試片ホルダー
７４ａ：試片挿入部
７４ｂ：試片ホルダー上部 71:Specimen 71a: One end 71b of the specimen: The other end 72 of the specimen: Cut 73: Score 74: Specimen holder 74a: Specimen insertion part 74b: Upper part of the specimen holder
７１ａ：試片の一方の端部
７１ｂ：試片の他方の端部
７２：切れ目
７３：スコア
７４：試片ホルダー
７４ａ：試片挿入部
７４ｂ：試片ホルダー上部 71:
Claims (13)
- 硫酸及び硫酸錫を含む硫酸錫めっき浴中のＳｎ濃度を３０～１２０ｇ／Ｌ、
該硫酸錫めっき浴の温度を２０～６０℃、
該硫酸錫めっきにおける電流密度を２～５０Ａ／ｄｍ２、
の範囲で調整して、鋼板表面上に占める錫面積率を５～９５％とし、
鋼板表面の鉄の一部を露出させるように鋼板表面に金属錫を被覆することを特徴とする表面処理鋼板の製造方法。 Sn concentration in a tin sulfate plating bath containing sulfuric acid and tin sulfate is 30 to 120 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.
The current density in the tin sulfate plating is 2 to 50 A / dm 2 ,
In this range, the tin area ratio on the steel sheet surface is 5 to 95%,
A method for producing a surface-treated steel sheet, wherein the steel sheet surface is coated with metallic tin so that a part of iron on the steel sheet surface is exposed. - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を３０～５０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２Ａ／ｄｍ２以下とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 30-50 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 A / dm 2 or less. - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を３０～５０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を４０～６０℃、
前記硫酸錫めっきにおける電流密度を２～５Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 30-50 g / L,
The temperature of the tin sulfate plating bath is 40-60 ° C.
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 5 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～５Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 5 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２～７Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 7 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を５０～７０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を５０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 50 to 70 g / L,
The temperature of the tin sulfate plating bath is 50-60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 10 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～７Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 7 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を３０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 30-60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 10 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を７０～９０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を５０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１５Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 70 to 90 g / L,
The temperature of the tin sulfate plating bath is 50-60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 15 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を９０～１２０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を２０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１０Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 90 to 120 g / L,
The temperature of the tin sulfate plating bath is 20 to 60 ° C.,
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 10 A / dm 2 . - 請求項１に記載の表面処理鋼板の製造方法において、
前記硫酸錫めっき浴中のＳｎ濃度を９０～１２０ｇ／Ｌ、
前記硫酸錫めっき浴の温度を４０～６０℃、
前記硫酸錫めっきにおける電流密度を２～１５Ａ／ｄｍ２とすることを特徴とする表面処理鋼板の製造方法。 In the manufacturing method of the surface-treated steel sheet according to claim 1,
Sn concentration in the tin sulfate plating bath is 90 to 120 g / L,
The temperature of the tin sulfate plating bath is 40-60 ° C.
A method for producing a surface-treated steel sheet, wherein a current density in the tin sulfate plating is 2 to 15 A / dm 2 . - 前記請求項１～１１いずれかに記載の製造方法によって製造された表面処理鋼板上に、樹脂を被覆することを特徴とする樹脂被覆鋼板の製造方法。 A method for producing a resin-coated steel sheet, comprising coating a resin on the surface-treated steel sheet produced by the production method according to any one of claims 1 to 11.
- 前記樹脂被覆を錫の融点以上の温度で行うことを特徴とする請求項１２に記載の樹脂被覆鋼板の製造方法。 The method for producing a resin-coated steel sheet according to claim 12, wherein the resin coating is performed at a temperature equal to or higher than a melting point of tin.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201080046159.7A CN102612574B (en) | 2009-11-04 | 2010-09-27 | Method for producing surface-treated steel sheet |
| EP10828043.9A EP2497845A4 (en) | 2009-11-04 | 2010-09-27 | Method for producing surface-treated steel sheet |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-253360 | 2009-11-04 | ||
| JP2009253360A JP5419638B2 (en) | 2009-11-04 | 2009-11-04 | Manufacturing method of surface-treated steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2011055481A1 true WO2011055481A1 (en) | 2011-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2010/005800 WO2011055481A1 (en) | 2009-11-04 | 2010-09-27 | Method for producing surface-treated steel sheet |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2497845A4 (en) |
| JP (1) | JP5419638B2 (en) |
| CN (1) | CN102612574B (en) |
| WO (1) | WO2011055481A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2564149A (en) | 2017-07-05 | 2019-01-09 | Skf Ab | Electroplated cage for rolling element bearing |
| CN112410836A (en) * | 2020-10-16 | 2021-02-26 | 宝应县建飞工艺品厂 | Hardware surface treatment process |
| JP2022166365A (en) * | 2021-04-21 | 2022-11-02 | 三菱重工業株式会社 | Method for lifting/lowering long object in wind power generation apparatus |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207489A (en) * | 1994-01-13 | 1995-08-08 | Nippon Steel Corp | Tin plating bath |
| JPH10121286A (en) * | 1996-10-18 | 1998-05-12 | Nkk Corp | Production of tinned steel sheet excellent in tin peeling resistance |
| JPH1192989A (en) * | 1997-09-19 | 1999-04-06 | Kawasaki Steel Corp | Surface treated steel sheet excellent in seam weldability |
| JPH11254586A (en) * | 1998-03-06 | 1999-09-21 | Mitsubishi Plastics Ind Ltd | Highly corrosion-resistant can, barrel material, film-laminated steel plate, and manufacture thereof |
| JP2002285354A (en) | 2001-03-23 | 2002-10-03 | Toyo Kohan Co Ltd | Sn PLATED STEEL SHEET, RESIN COATED Sn PLATED STEEL SHEET OBTAINED BY COATING Sn PLATED STEEL SHEET WITH RESIN FILM, CAN USING THE STEEL SHEET AND METHOD FOR PRODUCING THE Sn PLATED STEEL SHEET AND RESIN-COATED Sn PLATED STEEL SHEET |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5647269B2 (en) * | 1972-08-11 | 1981-11-09 | ||
| JPS62124296A (en) * | 1985-11-25 | 1987-06-05 | Toyo Kohan Co Ltd | Surface treated steel sheet having excellent seam weldability and paint adhesiveness and its production |
| CA2019861C (en) * | 1990-06-26 | 1995-10-17 | Hiroaki Kawamura | Tin-plated steel sheet with a chromium bilayer and a copolyester resin laminate and method |
| AU9763898A (en) * | 1997-11-14 | 1999-06-07 | Toyo Kohan Co. Ltd. | Surface-treated steel sheet having lowered contact resistance and connecting terminal members made by using the same |
| JP4270768B2 (en) * | 2000-11-08 | 2009-06-03 | Ｊｆｅスチール株式会社 | Tin-plated steel sheet and chemical treatment liquid |
| WO2007091732A2 (en) * | 2006-02-09 | 2007-08-16 | Nippon Steel Corporation | Tinned steel sheet excellent in corrosion resistance |
-
2009
- 2009-11-04 JP JP2009253360A patent/JP5419638B2/en active Active
-
2010
- 2010-09-27 WO PCT/JP2010/005800 patent/WO2011055481A1/en active Application Filing
- 2010-09-27 CN CN201080046159.7A patent/CN102612574B/en not_active Expired - Fee Related
- 2010-09-27 EP EP10828043.9A patent/EP2497845A4/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207489A (en) * | 1994-01-13 | 1995-08-08 | Nippon Steel Corp | Tin plating bath |
| JPH10121286A (en) * | 1996-10-18 | 1998-05-12 | Nkk Corp | Production of tinned steel sheet excellent in tin peeling resistance |
| JPH1192989A (en) * | 1997-09-19 | 1999-04-06 | Kawasaki Steel Corp | Surface treated steel sheet excellent in seam weldability |
| JPH11254586A (en) * | 1998-03-06 | 1999-09-21 | Mitsubishi Plastics Ind Ltd | Highly corrosion-resistant can, barrel material, film-laminated steel plate, and manufacture thereof |
| JP2002285354A (en) | 2001-03-23 | 2002-10-03 | Toyo Kohan Co Ltd | Sn PLATED STEEL SHEET, RESIN COATED Sn PLATED STEEL SHEET OBTAINED BY COATING Sn PLATED STEEL SHEET WITH RESIN FILM, CAN USING THE STEEL SHEET AND METHOD FOR PRODUCING THE Sn PLATED STEEL SHEET AND RESIN-COATED Sn PLATED STEEL SHEET |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP2497845A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011099134A (en) | 2011-05-19 |
| CN102612574A (en) | 2012-07-25 |
| EP2497845A4 (en) | 2016-10-12 |
| CN102612574B (en) | 2014-08-20 |
| EP2497845A1 (en) | 2012-09-12 |
| JP5419638B2 (en) | 2014-02-19 |
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