WO2005068184A1 - 2ピース缶用ラミネート鋼板およびそれを用いた2ピース缶 - Google Patents
2ピース缶用ラミネート鋼板およびそれを用いた2ピース缶 Download PDFInfo
- Publication number
- WO2005068184A1 WO2005068184A1 PCT/JP2004/000218 JP2004000218W WO2005068184A1 WO 2005068184 A1 WO2005068184 A1 WO 2005068184A1 JP 2004000218 W JP2004000218 W JP 2004000218W WO 2005068184 A1 WO2005068184 A1 WO 2005068184A1
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- WIPO (PCT)
- Prior art keywords
- piece
- steel sheet
- tin
- resin film
- polyester resin
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
Definitions
- the present invention relates to a laminated steel sheet for two-piece cans and a two-piece can using the same for the purpose of obtaining a two-piece can particularly excellent in white color of a can wall.
- a coated metal plate that has been coated with a resin film on a metal plate in advance has been (1) drawn and ironed, (2) drawn and stretched (the can wall was bent and stretched at the curvature corners of the redrawing die, and the side wall was formed). (3) In the forming process by drawing and stretching, the process of thinning the can wall using ironing at the time of stretching is also used.
- the so-called two-piece cans which integrate and shape the walls, occupy a significant portion of beverage cans. In these two-piece cans formed by processing these coated metal plates, since the outer surface of the can is coated or printed, the surface of the coated metal plate that is to be the outer surface of the can is a resin containing a white pigment that serves as a printing base.
- TFS electrolytic oxalate-treated steel sheet
- TFS electrolytic oxalate-treated steel sheet
- the tint of the can wall is thinned because the color tone of the surface is based on the color tone of the blackish steel base material and the tint of the bluish chromium hydrated oxide film. And the metal plate base is not sufficiently concealed.
- the white color in the resin film Attempts have been made to increase the content of the pigment, but if the content is excessively large, it may be shaved during molding or the workability may be reduced and the film may be easily cracked. I can't let that happen.
- thinning of metal plates and resin films has progressed due to demand for can cost reduction, and it has become more difficult to obtain a good white tone on the outer surface of a two-piece can.
- Japanese Patent Application Laid-Open No. H11-091031 discloses that a biaxially stretched polyethylene terephthalate / isophthalate copolymer film is provided on the inner side of a can of TFS, and titanium oxide is provided on a side of the outer side of the can.
- An organic coated metal plate coated with a biaxially oriented polyethylene terephthalate isophthalate copolymer film containing 30% by weight is drawn and stretched to form a deep drawn cup, and then aluminum flakes or aluminum flakes are formed on the outer surface.
- a paint containing mica is applied to compensate for the hiding power or lack of white color, and that a can with a prominent glitter can be obtained. After forming into a can, it must be painted in a separate process and then baked and dried, requiring large-scale equipment in addition to the forming equipment. Absent.
- Japanese Patent Application Laid-Open No. 2000-1546464 discloses an aluminum alloy, TFS, or glazing metal plate in which one layer contains two or more types of coloring pigments. It discloses a two-piece can that is coated with a colored polyester resin composed of at least two layers, and is subjected to ironing as well as drawing and stretching. The two-piece can is said to be rich in design and to conceal the color tone of the underlying metal substrate, thereby omitting painting. In order to form multi-layer films in this manner, it is necessary to prepare many types of master batches composed of resin pellets containing various types of pigments, and also to form the same film.
- the metal plate substrate can be sufficiently concealed on the outer surface side of the can, and a good white tone can be exhibited. It is an object of the present invention to provide a laminated steel sheet for two-piece cans and a two-piece can using the same. Disclosure of the invention
- the laminated steel sheet for two-piece cans of the present invention that solves the above-mentioned problems is a laminated steel sheet comprising a tin-plated steel sheet coated with a transparent polyester resin film on one side and a white polyester resin film on the other side.
- Laminated steel sheet for two-piece cans with a Hunter L value of 78 or more measured by a colorimeter on the resin film-coated surface.
- the tin-plated steel sheet is treated with molten tin after electroplating tin.
- Tin-plated steel sheet, or tin-plated steel sheet that is not tin-plated and is electroplated with tin and transparent polyester resin film and white polyester resin
- the film is a non-oriented film, and the white polyester resin film further comprises 5 to 30% by weight of a white pigment.
- the two-piece can of the present invention is formed by subjecting any one of the above-described laminated steel sheets for two-piece can to a drawing and ironing process so that the white polyester resin film-coated surface is on the outer surface of the can.
- a two-piece can with a Hunter L value of 75 or more measured by a colorimeter on the outer wall of the can, or any one of the above laminate steel plates for two-piece cans is made of white polyester
- a two-piece can formed by drawing and stretching with the resin film-covered surface facing the outside of the can the hunter's L measured with a colorimeter on the can wall on the outside of the can was measured.
- a two-piece can with a value of 75 or more, or a laminated steel sheet for any of the above two-piece cans, is drawn and processed such that the white polyester resin film-coated surface is on the outer surface of the can.
- the Hunter's L value measured by a colorimeter on the outer wall of the can is 75 or more.
- the upper end of the can is drawn to provide an opening end having a diameter smaller than the bottom diameter of the can, and further, a screw is provided at the opening end.
- a screw portion for attaching a cap is provided.
- the laminated steel sheet for two-piece cans according to the present invention is obtained by coating a white polyester resin film for the outer surface of a can on a mirror surface treated with molten tin after tinning or a pearlescent surface not treated with molten tin. And exhibits a good white tone. Therefore, the laminated steel sheet for 2-piece cans of the present invention is simultaneously drawn and drawn, drawn and stretched, drawn and stretched so that the white polyester resin film-coated surface becomes the outer surface of the can. Good whiteness can be maintained even on the outer wall of the can of the two-piece can where the white polyester film on the wall of the can is thinned by forming into a two-piece can by applying ironing or it can.
- a tin-plated steel sheet is used as a base steel sheet covering the resin film.
- the tin-plated steel sheet can be obtained by degreasing and pickling a cold-rolled steel sheet using a conventional method, and then plating the tin using a known electric plating method.
- Most of the commercially available tin-plated steel sheets are tin-plated and heated to a temperature equal to or higher than the tin melting temperature to melt tin and mirror-finish.
- tin-plated steel sheet for the resin film-coated base of the laminated steel sheet for two-piece cans of the present invention a tin-plated steel sheet subjected to such a molten tin treatment and mirror-finished may be used. It is also possible to use a tin-plated steel sheet that has been subjected to electrical plating without being subjected to the molten tin treatment after the plating.
- a tin-plated steel plate that has been treated with molten tin and mirror-finished is coated with a white polyester resin
- the tin-plated surface that is not subjected to the molten tin treatment has a beautiful pearl luster, and the pearl luster of the base is maintained even when a white polyester resin film is coated on it and molded into a two-piece can.
- the tin plating amount is preferably 0.2 to: L 1.2 g Zm 2 .
- a surface treatment for improving the adhesion to the resin film is performed on the molten tin-treated tin-plated steel sheet or the unmelted tin-treated tin-plated steel sheet prepared as described above.
- As the surface treatment a method of forming a chromium hydrated oxide film on tin plating by immersion treatment in an aqueous solution of dichromate or electrolytic treatment, and electrolytic treatment in an aqueous solution of chromic anhydride, A method of forming a two-layer film consisting of chromium metal and hydrated chromium oxide on tin plating, a method of forming a thin layer of organic resin such as polyacrylic acid and epoxy resin on tin plating, and tin plating
- a silane coupling treatment it is preferable to perform a silane coupling treatment because good adhesion to a resin film is obtained, and the treatment is simple and economical.
- the silane coupling treatment may be performed after tin plating on the steel sheet, or after the tin plating and molten tin treatment, or may be formed on the tin plating layer surface before the silane coupling treatment. It may be carried out after performing a treatment for removing the tin oxide film thus formed.
- the treatment to remove the tin oxide film includes cathodic electrolytic treatment in an aqueous solution of an alkali metal or ammonium carbonate or bicarbonate, and immersion treatment in a mixed aqueous solution of sodium chlorite, sodium phosphate and sodium hydroxide.
- a silane coupling agent is applied to the surface of the tin-plated steel plate or the tin-plated steel plate that has been treated to remove the tin oxide film, and dried.
- the silane coupling agent there are various types such as a bull type, an acrylic type, an epoxy type, an amino type, a mercapto type and a chloropropyl type, and it is preferable to use an amino type silane coupling agent. .
- silane coupling agent of the amino type there can be used, for example, aminopropyltrimethoxysilane, aminopropylmethylethoxysilane, aminopropyltriethoxysilane, and phenylaminopropyltrimethoxysilane.
- a 5 to 200 g / L aqueous solution of these silane coupling agents is applied to the surface of the tin-plated steel sheet and dried.
- a coating method a known dipping method, a roll coating method, a squeezing method using a roll after dipping, a spray method, or an electric field treatment method can be applied.
- Coating amount after drying is preferably in Kei elementary quantity measured by a fluorescent X-ray method is 1 ⁇ 5 O mg / m 2. In this way, the base steel sheet coated with the resin film of the laminated steel sheet for two-piece cans of the present invention is obtained.
- polyester resins used for transparent and white films include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalene Dicarboxylic acid, diphenylcarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfoncarboxylic acid, anthracenedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4- Cyclohexanedicarboxylic acid, Hexahydroterephthalenoic acid, Hexahydr
- a homopolymer obtained by polycondensation of one or more diols a copolymer obtained by polycondensation of one or more dicarboxylic acids and two or more diols, or a homopolymer obtained by polycondensation of two or more diols and one or more diols
- Any polyester resin of the blend resin obtained by rendering may be used.
- the copolyester resin mainly composed of terephthalic acid and isophthalic acid as the acid component has the property of maintaining the workability and mechanical properties and the flavor of the contents filled in the can without changing the flavor. It is particularly preferable in view of the above.
- the homopolymer and copolymer polyester resins need to have a molecular weight within a range capable of being formed into a film, and were measured using a phenol / tetrachloroethane mixed solvent. It is preferable that the intrinsic viscosity [ ⁇ ] is in the range of 0.5 to 1.6, particularly 0.6 to 1.5.
- Films formed from these polyester resins can be stretched uniaxially or biaxially and heat-set.Oriented films can be heated and melted and extruded from a die without stretching.
- any of non-oriented films may be used, in the present invention, it is preferable to use a non-oriented film.
- the non-oriented polyester resin film can be thermally bonded to a tin-plated steel sheet at a temperature of 23 ° C. or lower, which is the melting temperature of tin, depending on the resin composition.
- an unoriented polyester resin film must be used for a tin-plated steel sheet having a pearlescent tin-plated layer, which has not been subjected to the molten tin treatment.
- a tin-plated steel sheet having a mirror tin-plated layer subjected to a molten tin treatment is coated with a polyester resin film.
- a tin-plated steel sheet is heated to a temperature equal to or higher than the melting temperature of tin, and a polyester resin film is brought into contact with the molten tin surface and pressed, a good adhesive strength cannot be obtained. From the above points, it is preferable to use a non-oriented film for the transparent polyester resin film and the white polyester resin film used for the laminated steel sheet for two-piece cans of the present invention.
- a white polyester resin film is prepared by mixing a white resin pellet containing a white pigment made of titanium oxide and a transparent resin pellet so as to have a desired pigment content, heating and dissolving, extruding and forming a film. can get.
- the white polyester resin film preferably contains 5 to 30% by weight of a white pigment. If the content is less than 5% by weight, a good white tone with an L value of 78 or more cannot be obtained in the laminated steel sheet for two-piece cans. A good white tone with the above L value cannot be obtained. If the white pigment is contained in an amount exceeding 30% by weight, shaving occurs when forming into a two-piece can or cracks occur in the film.
- the thickness of the transparent polyester resin is 10 from the viewpoint of corrosion resistance and permeation resistance of the contents.
- the thickness of the white polyester resin is preferably 5 to 40 ⁇ from the viewpoint of obtaining a good white tone and economical efficiency.
- These transparent polyester resin film and white polyester resin film are thermally bonded to a tin-plated steel sheet as shown below. That is, using a known laminating apparatus, a tin-plated steel sheet is heated to a temperature equal to or lower than the melting point of tin, and a transparent polyester resin film is abutted on one side and a white polyester resin film is abutted on the other side. Using a roll, sandwich the three members and crimp them, immediately immerse them in water and quench. Thus, the laminated steel sheet for two-piece cans of the present invention can be obtained.
- the L value of the hunter measured by a colorimeter on the surface coated with the white polyester resin film is 78 or more. It is preferable that It is more preferably 83 to 88. If the L value is less than 78, a good white tone with an L value of 75 or more cannot be obtained in the can wall after forming into a two-piece can. It is extremely difficult to obtain an L value exceeding 8 8.
- the two-piece can of the present invention can be obtained by forming and applying the above-described laminated steel sheet for two-piece cans of the present invention.
- the forming methods include (1) drawing and ironing, (2) drawing and stretching (a method of bending and extending the can wall at the curvature corner of the redrawing die to reduce the thickness of the side wall), (3) )
- drawing and stretching a method of bending and extending the can wall at the curvature corner of the redrawing die to reduce the thickness of the side wall
- ironing is also used at the time of stretching to further reduce the thickness of the can wall. The following describes each addition method.
- a blank on a disc is punched out of a two-piece can laminated steel plate, and the blank is drawn into a shallow nip with the white film side facing the outside.
- the dies are formed into deep dies with the desired two-piece can diameter. Ironing the side wall of the die using thinning die with two or three steps continuously arranged with the deep die, thinning the side wall and increasing the height of the can. Form into an integrated two-piece can. Next, the upper part of the can is trimmed into a two-piece can of a certain height.
- the total ironing rate ((the thickness of the side wall after ironing at the final stage of this plate thickness and the original plate thickness) XI 00: (%)) is 50 to 70 %.
- a blank on a circular plate is punched out of a two-piece can laminated steel sheet, and the blank is drawn into a shallow cup with the white film side facing the outside.
- the shallow cup is redrawn by two-stage (primary, secondary) or three-stage (primary, secondary, tertiary) stretching to gradually reduce the diameter, and the desired two-piece can Into a two-piece can with an integrated bottom and wall of can diameter and height. Then, the top of the can Is trimmed into a two-piece can of a certain height.
- the total drawing ratio (blank diameter Z can diameter after redrawing at the final stage) is preferably from 2 ::! To 2.5.
- the L value of the hunter measured by a colorimeter on the outer surface of the can wall portion where the white resin film is thinned is 75 or more. If the L value is less than 75, a good white tone cannot be obtained. More preferably, it is 80 to 86. It is extremely difficult to obtain an L value exceeding 8 6 In a two-piece can formed in this way, the outer periphery near the opening at the top of the trimmed can is drawn and the bottom A two-piece can with an open end smaller than the diameter. Further, a screw portion for mounting a screw cap may be formed near the opening end portion by using a rolling method. Example
- the cold-rolled steel sheet having the thickness shown in Table 1 was subjected to electrolytic degreasing treatment and pickling treatment by a standard method, and then tin was electroplated on both sides thereof with a plating amount shown in Table 1 using a known ferrostan bath.
- Some of the plated sheets were heated to a temperature higher than the melting temperature of tin, and tin was heated and melted to a mirror finish.
- these tin-plated steel sheets were immersed in an aqueous solution of an amino-based silane coupling agent (KB M-903, manufactured by Shin-Etsu Chemical Co., Ltd.) at a concentration of 80 g / L, dried, and dried.
- a silane coupling agent coating layer was formed on the plating.
- the tin-plated steel sheet shown in Table 1 prepared as described above and TFS as a comparative material surface treatment film: amount of chromium metal: 9 O mg / m 2 , chromium hydrated oxidation
- the above-mentioned transparent resin film was heat-bonded to one side of the compound: 16 mg / m 2 ) and the above-mentioned white film was heat-bonded to the other side.
- a tin-plated steel sheet or TFS on which a silane coupling agent coating layer is formed is heated to 200 ° C., a transparent resin film is abutted on one side, and a white film is abutted on the other side, and the After three members were sandwiched and crimped using the crimping roll, they were immediately immersed in water and quenched. Then, the adhering water was dried to obtain a test material for laminated steel sheets for two-piece cans indicated by sample numbers 1 to 15 in Table 1.
- the white tone of the white polyester resin films of the test materials of Sample Nos. 1 to 15 obtained as described above was evaluated by the L value of Hunter. That is, the L value of the hunter was measured using a color difference meter (CR-300, manufactured by Minolta Camera Co., Ltd.), and the degree of white tone was evaluated based on the following criteria.
- the test material shown in Sample No. 1 15 was white-polished using the following three molding methods.
- the two-piece can was formed and processed with the ester resin coated surface facing the outside of the can, and the L-value of the hunter was determined by setting the degree of whiteness of the obtained white polyester resin film on the can wall in the same manner as the test plate.
- the degree of white tone was evaluated based on the following criteria. Table 2 shows the evaluation results.
- Curvature radius of curvature corner of redraw die 0.40mm
- Curvature radius of curvature corner of redrawing die 0.37mm
- the laminated steel sheet for a two-piece can of the present invention and the two-piece can of the present invention obtained by molding the same into a two-piece can exhibit a good white tone on the plate surface and the outer surface of the can. .
- the upper end of the can was drawn 35 mm, so that the diameter of the opening end was 40 mm, and the part 12 mm from the opening end was conical so that it became cylindrical, and the upper part was made cylindrical. No peeling of the resin film was observed on the outer surface. Further, a screw portion was formed at a portion 12 mm from the opening end by a rolling method, but no peeling of the resin film was observed at the screw forming portion.
- the laminated steel sheet for two-piece cans of the present invention has a mirror-finished Or a pearlescent surface that is not treated with molten tin and coated with a white polyester resin film for the outer surface of the can. Even if the tin-plated steel plate that has been subjected to the molten tin treatment and is mirror-finished is coated with a white polyester resin film and formed into a two-piece can, the white polyester film on the can wall is thinned even when the white polyester film is thinned. However, unlike the TFS, the underlying metal does not show through and does not have poor concealment.
- the tin-plated surface that is not subjected to the molten tin treatment has a beautiful pearl luster, and even if it is coated with a white polyester resin film and formed into a two-piece can, the pearl luster of the base is maintained, and Even when the white polyester film on the wall is thinned, the whiteness of the film and the pearly luster of tin are combined, and the white tone does not decrease as in TFS.
- a resin film is thermally bonded to a tin-plated steel sheet that has been subjected to a silane coupling treatment. Absent. Therefore, any of the drawing and ironing, drawing and stretching, and the drawing and ironing simultaneously with the drawing can be performed to form a two-piece can and the resin film does not peel off. The resin film does not peel off even if the upper part of the two-piece can is subjected to a drawing process to reduce the diameter or a thread is formed.
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PCT/JP2004/000218 WO2005068184A1 (ja) | 2004-01-15 | 2004-01-15 | 2ピース缶用ラミネート鋼板およびそれを用いた2ピース缶 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2021157572A1 (ja) * | 2020-02-03 | 2021-08-12 | 東洋製罐グループホールディングス株式会社 | 塗料組成物、塗装金属板、並びに、絞りしごき缶及びその製造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0824958A (ja) * | 1994-07-14 | 1996-01-30 | Toyo Kohan Co Ltd | 2ピース缶用樹脂被覆鋼板 |
JPH10168202A (ja) * | 1996-12-06 | 1998-06-23 | Teijin Ltd | ポリエステルフィルム |
JPH11140691A (ja) * | 1997-11-14 | 1999-05-25 | Toyo Kohan Co Ltd | 鋼板の表面処理方法、表面処理鋼板、および表面処理鋼板を用いた熱可塑性樹脂被覆鋼板 |
JP2004098552A (ja) * | 2002-09-11 | 2004-04-02 | Toyo Kohan Co Ltd | 2ピース缶用ラミネート鋼板およびそれを用いた2ピース缶 |
-
2004
- 2004-01-15 WO PCT/JP2004/000218 patent/WO2005068184A1/ja active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0824958A (ja) * | 1994-07-14 | 1996-01-30 | Toyo Kohan Co Ltd | 2ピース缶用樹脂被覆鋼板 |
JPH10168202A (ja) * | 1996-12-06 | 1998-06-23 | Teijin Ltd | ポリエステルフィルム |
JPH11140691A (ja) * | 1997-11-14 | 1999-05-25 | Toyo Kohan Co Ltd | 鋼板の表面処理方法、表面処理鋼板、および表面処理鋼板を用いた熱可塑性樹脂被覆鋼板 |
JP2004098552A (ja) * | 2002-09-11 | 2004-04-02 | Toyo Kohan Co Ltd | 2ピース缶用ラミネート鋼板およびそれを用いた2ピース缶 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021157572A1 (ja) * | 2020-02-03 | 2021-08-12 | 東洋製罐グループホールディングス株式会社 | 塗料組成物、塗装金属板、並びに、絞りしごき缶及びその製造方法 |
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