US20030039778A1 - Resin-coated seamless can - Google Patents

Resin-coated seamless can Download PDF

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Publication number
US20030039778A1
US20030039778A1 US10/178,790 US17879002A US2003039778A1 US 20030039778 A1 US20030039778 A1 US 20030039778A1 US 17879002 A US17879002 A US 17879002A US 2003039778 A1 US2003039778 A1 US 2003039778A1
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United States
Prior art keywords
resin
polyester resin
coated
seamless
resin layer
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Abandoned
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US10/178,790
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English (en)
Inventor
Kazuhiro Sato
Kazuaki Ohashi
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Toyo Seikan Group Holdings Ltd
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Toyo Seikan Kaisha Ltd
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Filing date
Publication date
Priority claimed from JP2001192047A external-priority patent/JP4411802B2/ja
Priority claimed from JP2001211430A external-priority patent/JP2003026138A/ja
Application filed by Toyo Seikan Kaisha Ltd filed Critical Toyo Seikan Kaisha Ltd
Assigned to TOYO SEIKAN KAISHA, LTD. reassignment TOYO SEIKAN KAISHA, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OHASHI, KAZUAKI, SATO, KAZUHIRO
Publication of US20030039778A1 publication Critical patent/US20030039778A1/en
Priority to US12/135,005 priority Critical patent/US8268422B2/en
Abandoned legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/12—Cans, casks, barrels, or drums
    • 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
    • B32B15/09—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 comprising polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/12—Cans, casks, barrels, or drums
    • B65D1/14—Cans, casks, barrels, or drums characterised by shape
    • B65D1/16—Cans, casks, barrels, or drums characterised by shape of curved cross-section, e.g. cylindrical
    • B65D1/165—Cylindrical cans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1303—Paper containing [e.g., paperboard, cardboard, fiberboard, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y10T428/1359—Three or more layers [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article

Definitions

  • the present invention relates to a resin-coated seamless can, and more particularly to a resin-coated seamless can which exhibits excellent corrosion resistance and excellent shock resistance.
  • a side seamless can there has been known a can which is produced by a following method. That is, a metal blank such as an aluminum plate, a tin plate or a tin-free steel plate is subjected to at least one drawing stage.
  • the drawing stage is conducted between a drawing die and a punch to form a cylindrical cup comprising a barrel portion free of seams on a side surface thereof and a bottom portion integrally connected to the barrel portion which is also free of seams.
  • the barrel portion may be subjected to ironing between an ironing punch and a die to reduce the thickness of the barrel portion (drawing/ironing working).
  • Methods for coating an organic resin film onto the side seamless can include a method of applying an organic coating onto a formed can which is a common and widely used technique and, in addition, a method of laminating a resin film onto a metal blank before a can is formed. Further, in the production of a can by thinning drawing forming, the use of a metal sheet coated with polyester, vinyl organosol, epoxy, phenolic or acryl has been known in the art.
  • thermoplastic resin film typically made of thermoplastic polyester onto a metal substrate For example, there have been adopted a method which laminates a biaxially stretched film onto a metal substrate using heat-bonding directly or by way of a primer layer for adhesion (for example, Japanese Laid-open Patent Publication 101930/1991, Japanese Laid-open Patent Publication 4229/1993, Japanese Laid-open Patent Publication 172556/1994) and a method which extrudes molten resin and coats the molten resin onto a metal substrate (Japanese Laid-open Patent Publication 86308/1998).
  • the resin-coated metal sheet for for can use which is produced by extruding and coating molten resin on a metal substrate or by laminating a cast film to the metal substrate, since the resin is held in the non-oriented state, the tolerance for endurance against the above-mentioned harsh working is large. Due to such a reason, the resin-coated metal sheet f or can use which is produced by extruding and coating molten resin on a metal substrate or by laminating a cast film to the metal substrate has been recently us ed.
  • thermoplastic resin-coated metal sheet which is produced by extruding molten resin onto the metal substrate or by laminating the cast film to the metal substrate is formed into a cylindrical cup by drawing forming. Thereafter, a seamless can which has a large height and can reduce a thickness of a side wall thereof is formed by thinning drawing forming and/or ironing working. Such a seamless can largely differs between a can bottom portion and a can barrel portion with respect to the state of an adhesive interface formed between a coated resin layer and the metal substrate.
  • dent resistance which is measured when the resin-coated metal sheet is formed into an actual canned product.
  • This dent resistance is the property which the resin-coated metal sheet is required to have. That is, the dent resistance is the property which ensures the resin-coated metal sheet to completely maintain the adhesiveness of the film and the protection even when an indentation called a dent is formed in the canned product due to a fall of the canned product or a collision of canned products.
  • a resin-coated seamless can which is formed of a resin-coated metal sheet produced by coating thermoplastic resin on a surface of a metal substrate and exhibits the excellent corrosion resistance and the excellent shock resistance.
  • the present invention is directed to a resin-coated seamless can formed of a resin-coated metal sheet which is produced by coating a polyester resin layer containing polyethylene terephthalate on a surface of a metal substrate, wherein the density of the polyester resin layer at a can inner-surface side is equal to or more than 1.36 at an upper portion of a can barrel portion or a can-barrel upper portion.
  • the density of the polyester resin layer at the can inner surface side is equal to or less than 1.36 at a can bottom portion.
  • the present invention is also directed to a resin-coated seamless can formed of a resin-coated metal sheet which is produced by coating a polyester resin layer containing polyethylene terephthalate on a surface of a metal substrate, wherein an infrared dichroic ratio (R1) of the polyester resin layer at the inner surface side of the can barrel portion which is expressed by a following formula (1) is set to equal to or more than 1.1.
  • R1 infrared dichroic ratio
  • Iw( ⁇ ) is an infrared absorption intensity of 973 cm ⁇ 1 with respect to polarized infrared rays perpendicular to the can height direction at the can barrel portion and Iw( ⁇ ) is an infrared absorption intensity of 973 cm ⁇ 1 with respect to polarized infrared rays parallel to the can height direction at the can barrel portion.
  • an infrared dichroic ratio (R2) of the polyester resin layer at the inner surface side of the can bottom portion expressed by a following formula (2) is set to equal to or less than 1.1.
  • IB( ⁇ ) is an infrared absorption intensity of 973 cm ⁇ 1 with respect to polarized infrared rays perpendicular to the metal substrate rolling direction at the can bottom portion and IB( ⁇ ) is an infrared absorption intensity of 973 cm ⁇ 1 with respect to polarized infrared rays parallel to the metal substrate rolling direction at the can bottom portion.
  • the resin-coated metal sheet by forming the non-oriented polyester resin layer on the metal substrate.
  • the resin-coated seamless can of the present invention is formed by drawing/thinning drawing forming and/or ironing working such that a thickness of the can barrel portion becomes 20 to 85% of a thickness of the can bottom portion.
  • the polyester rein layer is constituted of two layers, wherein a surface layer (A) is formed of polyethylene terephthalate/isophthalate containing equal to or less than 15 mol % of isophthalic acid and a lower layer (B) is formed of polyethylene terephthalate/isophthalate containing 8 to 25 mol % of isophthalic acid.
  • the intrinsic viscosity of the polyester resin is set to equal to or more than 0.6 dl/g.
  • the degree of crystallization due to a density method of the polyester resin layer at an upper portion of the can barrel portion falls in a range of 20 to 55%.
  • FIG. 1 is a schematic view showing a resin-coated seamless can according to the present invention.
  • FIG. 2 is a schematic cross-sectional view of a resin-coated metal sheet used in the present invention.
  • FIG. 3 is a schematic cross-sectional view of another resin-coated metal sheet used in the present invention.
  • a resin-coated seamless can according to the present invention is formed by making a resin-coated metal sheet which is formed by coating a polyester resin layer containing polyethylene terephthalate onto a surface of a metal substrate subjected to drawing/thinning drawing forming and/or ironing working.
  • the resin-coated seamless can according to the present invention is formed such that the above-mentioned polyester resin-coated metal sheet is drawn into a bottomed cup using a drawing die and a punch and, thereafter, the cup-shaped metal sheet is subjected to thinning drawing forming by bending and elongation and/or ironing working.
  • FIG. 1 is a schematic view showing one embodiment of the resin-coated seamless can according to the present invention.
  • a resin-coated seamless can 10 is formed by making the resin-coated metal sheet 1 subjected to the drawing/thinning drawing forming and/or ironing working and is constituted of a can bottom portion 11 and a can barrel portion 12 .
  • the can barrel portion 12 includes a straight portion consisting of two halves defined in the vertical direction, wherein an upper half of the straight portion constitutes a can-barrel upper portion 15 and a lower half constitutes a can-barrel lower portion 16 .
  • a neck portion 13 is formed when necessary. Further, a flange portion 14 is formed on the upper end of the can barrel portion 12 by way of the neck portion 13 .
  • a polyester resin layer 3 of the can barrel portion 12 is held in the state that molecules thereof are oriented at least in the uniaxial direction, while the polyester resin layer 3 of the can bottom portion 11 is held in the state that molecules are oriented in no direction.
  • the degree of working of the can barrel upper portion 15 at the time of forming the can is relatively high compared to that of the can-barrel lower portion 16 so that it is considered that defects of the coated resin is more liable to be generated in the can-barrel upper portion 15 . Accordingly, it is considered that by controlling the characteristic of the resin-coated seamless can at least at the can-barrel upper portion 15 , the stability of the quality of the whole can can be ensured.
  • the resin-coated seamless can 10 according to the present invention may be produced by coating the polyester resin layers 3 on both surfaces of the metal substrate 2 .
  • the resin-coated metal sheet 1 having the cross-sectional structure shown in FIG. 2 in which the polyester resin layers 3 , 4 are coated on both surfaces of the metal substrate 2 is formed by drawing/thinning drawing forming and/or ironing working.
  • the resin-coated seamless can 10 according to the present invention may have the cross-sectional structure shown in FIG. 3, wherein an inner surface layer 5 is formed as an upper layer of the inner-surface polyester resin layer 3 .
  • Such an inner surface layer 5 is formed on an inner surface side of the resin-coated seamless can 10 .
  • the inner surface layer 5 is preferably formed of resin which exhibits a poor absorption property for fragrance components in the inside of a content, for example.
  • the resin-coated seamless can 10 according to the present invention is characterized in that the density of the polyester resin layer 3 at the inner surface side in the can barrel portion 12 is set to equal to or more than 1.36 at the can-barrel upper portion.
  • the density is less than 1.36, the corrosion under film is liable to be generated when an acid content is filled in the formed seamless can. Further, the adhesiveness of the polyester resin layer with the metal substrate and the dent resistance of the polyester resin layer are degraded. Accordingly, such a density is not desirable.
  • the density of the polyester resin layer at the inner-surface side of the can barrel portion indicates the degree of crystallization.
  • the resin-coated seamless can according to the present invention is characterized in that the density of the polyester resin layer containing polyethylene terephthalate at the inner surface of the can barrel portion is maintained at a value equal to or more than 1.36 and the molecules are oriented at the can-barrel upper portion.
  • the resin-coated seamless can 10 according to the present invention is characterized in that an infrared dichroic ratio (R1) of the inner surface side polyester resin layer 3 at the can barrel portion 12 is set to equal to or more than 1.1.
  • the infrared dichroic ratio (R1) is less than 1.1, corrosion under film is liable to be generated when an acid content is filled in the formed seamless can. Further, adhesiveness of the polyester resin layer with the metal substrate and dent resistance are also degraded. Accordingly, such a dichroic ratio is not desirable.
  • the infrared dichroic ratio (R1) of the polyester resin layer at the inner surface side of the can barrel portion which is expressed by a following formula (1) indicates a ratio between an infrared absorption intensity Iw( ⁇ ) of 973 cm ⁇ 1 of the polyester resin layer at the inner surface side of the can barrel portion with respect to polarized infrared rays perpendicular to the can height direction and an infrared absorption intensity Iw( ⁇ ) of 973 cm ⁇ 1 of the polyester resin layer at the inner surface side of the can barrel portion with respect to polarized infrared rays parallel to the can height direction.
  • the resin-coated seamless can according to the present invention is characterized in that in the polyester resin layer containing polyethylene terephthalate formed on the inner surface of the can barrel portion, the ratio (R1) between the infrared absorption intensity Iw( ⁇ ) of 973 cm ⁇ 1 of the polyester resin layer at the inner surface side of the can barrel portion with respect to polarized infrared rays perpendicular to the can height direction and the infrared absorption intensity Iw( ⁇ ) of 973 cm ⁇ 1 of the polyester resin layer at the can barrel portion with respect to polarized infrared rays parallel to the can height direction is set to equal to or more than 1.1 and molecules thereof are subjected to orientation.
  • the density of the polyester resin layer at the inner surface side of the can bottom portion or the inner surface side of the can bottomed portion and the inner surface side of the can-barrel lower portion is set to equal to or less than 1.36.
  • the orientation state of the resin-coated layer at the can bottom portion shows the orientation state of the resin-coated layer before working. Accordingly, to enable the resin-coated layer at the can bottom portion to follow the severe working of the can barrel portion, it is necessary to maintain the orientation state of the coated resin layer at the can bottom portion substantially in the non-oriented state. Further, it is possible to maintain corrosion resistance, shock resistance and the like in the satisfying state by sufficiently ensuring adhessiveness on the adhesive interface formed between the resin-coated layer and the surface of the metal substrate at the can bottom portion.
  • the endowment of the above-mentioned characteristics on density of the resin-coated seamless can be conducted in view of the orientation state of the coated polyester resin before working, the forming condition of the seamless can, the heat treatment after forming the seamless can and the like.
  • the substantially non-oriented polyester resin-coated metal sheet which is produced by extruding and coating molten resin on a surface of a metal sheet or laminating a cast film on the surface of the metal sheet is used.
  • the resin-coated metal sheet is formed into a seamless cap by thinning drawing forming and/or ironing working under an appropriate temperature condition. Thereafter, the seamless cap is subjected to the heat treatment so that a strain (a residual stress) of the coated resin layer of the can barrel portion which is caused by working is alleviated and the molecules are orientated and crystallized.
  • the coated resin layer of the can bottom portion is in the non-oriented state. It is also preferable that with respect to the polyester resin layer on the inner surface of the can bottom portion which contains polyethylene terephthalate, a ratio (R2) between an infrared absorption intensity IB( ⁇ ) of 973 cm ⁇ 1 with respect to polarized infrared rays perpendicular to the metal substrate rolling direction at the can bottom portion and an infrared absorption intensity IB( ⁇ ) of 973 cm ⁇ 1 with respect to polarized infrared rays parallel to the metal substrate rolling direction at the can bottom portion is set to equal to or less than 1.1.
  • the orientation state of the coated resin layer is maintained so that the orientation state of the can bottom portion indicates the orientation state of the coated resin layer before working.
  • the above-mentioned dichroic ratio R2 is set to equal to or less than 1.1 which shows that the coated resin layer is substantially in the non-oriented state.
  • the adhesive interface between the coated resin layer and the surface of the metal substrate is substantially maintained in a form of the resin-coated metal sheet before working and hence, the adhesiveness between them is sufficient and the can bottom portion is maintained in the state which satisfies the corrosion resistance and the shock resistance.
  • the endowment of the above-mentioned characteristics on the infrared dichroic ratios (R1) and (R2) of the resin-coated seamless can be conducted in view of the orientation state of the coated polyester resin before working, the forming condition of the seamless can, the heat treatment after forming the seamless can and the like.
  • the substantially non-oriented polyester resin-coated metal sheet which is produced by extruding and coating molten resin on a surface of a metal sheet or laminating a cast film on the surface of the metal sheet is used.
  • the resin-coated metal sheet is formed into a seamless cap by thinning drawing forming and/or ironing working under the appropriate temperature condition. Thereafter, the seamless cap is subjected to the heat treatment so that the strain (the residual stress) of the coated resin layer of the can barrel portion which is caused by working is alleviated and the molecular orientation is thermally fixed.
  • the heat treatment it is preferable to perform the heat treatment in general at a temperature of Tg+50 degree centigrade with respect to a glass transition point (Tg) of the resin-coated layer. It is particularly preferable to perform the heat treatment in a temperature range of Tg+100 to a melting point (Tm) ⁇ 5 degree centigrade. This is because that when the temperature of the heat treatment is at a temperature side lower than the above-mentioned temperature range, there arises a problem that the alleviation of strain of the coated polyester resin layer becomes insufficient and there is a possibility that the post workability is degraded.
  • the heat resistance of the coated polyester resin layer is enhanced and the adhesiveness of the coated polyester resin layer to the metal substrate is also enhanced. Further, workability which influences post workings such as neck-in working, flange working and the like or flavor resistance can be enhanced.
  • the density of the resin-coated seamless can at the inner surface side of the can bottom portion or the inner surface side of the can bottom portion and the inner surface side of the can-barrel lower portion can be maintained at a value equal to or below 1.36.
  • the resin-coated layer is of a multiple layer consisting of two or more layers, it is preferable to perform the heat treatment such that the temperature of the lowermost resin-coated layer falls in the above-mentioned temperature range.
  • the polyester resin layer of the resin-coated seamless can according to the present invention is characterized by mainly having the latter crystallization characteristics.
  • the polyester resin layer of the can-barrel upper portion is highly subjected to the orientation crystallization at the time of forming the seamless can and, due to the heat treatment performed thereafter, it is possible to impart the excellent characteristics with respect to heat resistance, shock resistance and corrosion resistance without giving rise to coarse lamella-type crystals.
  • the above-mentioned heat treatment manipulation is performed before or after performing trimming which cuts lug portions of can which are produced at the time of forming the seamless can.
  • the necessary heat treatment time differs also depending on the degree of molecular orientation formed in the coated polyester resin layer of the can barrel portion at the time of forming the can, the heat treatment time is short in general and it is preferable to perform the heat treatment within 1 to 10 minutes.
  • the seamless can after the heat treatment, the seamless can may be gradually cooled or quenched.
  • the can barrel portion 12 at the can-inner-surface side of the resin-coated seamless can according to the present invention is subjected to the molecular orientation by working, since the level of working is not severe with respect to the can bottom portion 11 , the coated resin layer of the can bottom portion is held at the non-oriented state so that the adhesive interface thereof with the metal substrate 2 substantially remains unchanged.
  • the thickness of the resin-coated seamless can 10 according to the present invention is preferably reduced by the drawing forming and subsequent thinning drawing forming and/or ironing working due to bending and elongation such that the thickness of the can barrel portion 12 becomes 20 to 85% of, preferably 40 to 80% of the thickness of the can bottom portion 11 .
  • polyester resin layer 3 of the can barrel portion 12 of the resin-coated seamless can 10 which is formed by drawing/thinning drawing forming and/or ironing working, two types of molecular orientations are provided.
  • the first molecular orientation makes the molecules of polyester resin oriented in the can axis (can height) direction along with the plastic flow at the time of performing drawing/thinning drawing forming and/or ironing working. This molecular orientation is similar to the fiber orientation.
  • the second molecular orientation is intrinsic to the ironing and, as described in Japanese Patent Publication 2970459, the benzene ring surfaces of the polyester molecules are oriented in the state substantially parallel to the film surface.
  • polyester resin used for producing the resin-coated seamless can according to the present invention should have the molecular weight sufficient to form a thin film layer on the metal substrate and it is preferable to use the polyester resin whose intrinsic viscosity (IV) is equal to or more than 0.6 dl/g, and more particularly in a range of 0.65 to 1.4 dl/g.
  • the polyester resin fails to have the heat resistance which can withstand various heat treatments, the formability to the seamless can and the workability to withstand the post working which will be performed after the forming operation. Further, the polyester resin whose intrinsic viscosity(IV) does not fall in the above-mentioned numerical value range cannot have the sufficient mechanical strength and exhibits insufficient barrier property to a corrosive component, and insufficient physical property to a canned content.
  • the polyester resin whose intrinsic viscosity (IV) falls in the above-mentioned numerical value range has a large molecular weight
  • the half-crystallization period (T) is long so that such polyester resin is also useful from a viewpoint of prevention of the thermal crystallization.
  • the polyester resin layer at the can barrel portion it is preferable to use resin whose molecules can be oriented as the polyester resin and to perform the working applied to the seamless can such that the orientation in at least one direction remains in the resin layer in the can barrel portion.
  • polyester resin layer laminated to the can inner surface side of the metal substrate it is preferable to use polyethylene terephthalate or polybutylene terephthalate. It is also preferable to use homogenous polyester such as polyethylene terephthalate.
  • the polyester resin layer it is preferable to lower the maximum degree of crystallization which the polyester resin layer can obtain from a viewpoint of the prevention of thermal crystallization and the enhancement of the shock resistance and the workability.
  • the prevention of the thermal crystallization and the enhancement of the shock resistance and the workability of the polyester resin layer can be also achieved by polymer blending or multi-layered lamination.
  • the copolymer polyester has a tendency to attenuate the uniaxial orientation which is generated at the time of forming the polyester resin layer onto the seamless can compared to homogeneous polyester.
  • the polyester resin layer used in the present invention may be formed of a multi-layered resin layer, wherein it is preferable that a surface layer (A) is formed of polyethylene terephthalate/isophthalate containing equal to or less than 15 mol % of isophthalic acid and a lower layer (B) is formed of polyethylene terephthalate/isophthalate containing 8 to 25 mol % of isophthalic acid.
  • the degree of crystallization of the polymer resin layer at the can barrel upper portion by the density method falls in a range of 20 to 55%.
  • the degree of crystallization (Xc) by the density method can be generally expressed by a following formula (3).
  • d indicates the density of a test piece (g/cm 3 ).
  • Resin blending agents which are known per se such as an antioxidant such as steric hindrance type phenol groups, an anti-block agent such as amorphous silica or the like, pigment such as titanium oxide (titanium white), various types of antistatic agents, a lubricant and the like can be blended into the polyester resin layer in accordance with known prescriptions.
  • the resin-coated metal sheet 1 served for producing the resin-coated seamless can 10 according to the present invention is produced by laminating the non-oriented polyester resin layer 3 to the metal substrate 2 .
  • the reason that the non-oriented polyester resin layer is used is that the resin-coated metal sheet can be produced with small number of steps and at a low cost by using a molten resin extrusion coating method or a stretched film (cast film) laminating method.
  • the reason that the resin-coated metal sheet 1 does not use a biaxially stretched film which has been conventionally used for manufacturing cans is that the working of the biaxially stretched film is difficult and pushes up a cost.
  • the resin-coated metal sheet 1 which is served for the present invention is produced by thermally bonding the polyester resin layer 3 which can orient molecules thereof in the non-stretched state to the metal substrate 2 .
  • the resin-coated metal sheet 1 is comprised of the metal substrate 2 and the polyester resin layer 3 which is positioned at least at the can inner-surface side.
  • the outer surface film 4 may be formed of material similar to that of the polyester resin layer 3 or may be formed of an ordinary paint for can use or an ordinary resin film.
  • FIG. 3 which shows another example of the cross-sectional structure of the resin-coated metal sheet, it is preferable to form the inner surface layer 5 on the polyester resin layer 3 which constitutes the can inner surface side.
  • the inner surface layer is formed of polyester or copolyester induced from a terephthalic acid component or an isophthalic component which exhibits a little absorbing property for a flavor component in the content and a lower layer is formed of copolyester having a large copolymer quantity such as isophtalic acid which exhibits the excellent adhesiveness to the metal substrate.
  • the resin-coated metal sheet 1 served for the present invention can be produced by extruding and coating the polyester resin layer 3 in the molten state onto the metal substrate 2 and thereafter thermally adhering the polyester resin layer 3 to the metal substrate 2 .
  • the resin-coated metal sheet 1 served for the present invention can be produced by thermally adhering a non-stretched film (cast film) made of polyester resin which is preliminarily formed into a film to the metal substrate 2 .
  • a non-stretched film made of polyester resin which is preliminarily formed into a film to the metal substrate 2 .
  • the thickness of the polyester resin layer 3 which is served for the present invention preferably falls in a range of 2 to 60 ⁇ m, and more particularly in a range of 3 to 40 ⁇ m as a whole from a viewpoint of the protective effect of metal and the workability.
  • an adhesive agent or a primer for adhesion may be used when necessary.
  • a metal substrate various kinds of surface treatment steel sheet or a light metal sheet made of aluminum or the like can be used.
  • the surface treatment steel sheet it is possible to use a sheet which is obtained by making a cold rolled steel sheet subjected to a secondary cold rolling after annealing and performing one, two or more kinds of surface treatments selected from a group consisting of zinc plating, tin plating, nickel plating, nickel-tin plating, electrolytic chromic-acid treatment, chromic acid treatment and the like.
  • an electrolytic chromic acid treatment sheet is named. It is particularly preferable to use the electrolytic chromic acid treatment sheet which includes a metal chromium layer of 10 to 200 mg/m 2 and a chromium oxide layer of 1 to 50 mg/m 2 (metal conversion). This electrolytic chromic acid treatment sheet exhibits the excellent adhesive property with respect to the resin film, the coating or the like and also exhibits the excellent corrosion resistance.
  • the surface treatment steel sheet is a hard tin sheet having a tin plating amount of 0.5 to 11.2 g/m 2 . It is preferable that an upper layer of the tin sheet is subjected to the chromic acid treatment or the chromic acid/phosphating treatment such that the chromium amount becomes 1 to 30 mg/m 2 in metal chromium conversion.
  • Still another preferred example of the surface treatment steel sheet is an aluminum coated steel sheet to which aluminum plating or the aluminum pressure bonding is applied.
  • an aluminum sheet or an aluminum alloy sheet can be used as the light metal sheet.
  • the aluminum alloy sheet which exhibits the excellent corrosion resistance and workability has the composition consisting of 0.2 to 1.5 weight % of Mn, 0.8 to 5 weight % of Mg, 0.25 to 0.3 weight % of Zn, 0.15 to 0.25 weight % of Cu and Al as the balance.
  • upper layers of these light metal sheets are also subjected to the chromic acid treatment or the chromic acid/phosphating treatment in which a chromium amount is 20 to 300 mg/m 2 in metal chromium conversion.
  • the surface treatment applied to the light metal sheet can be performed by using water-soluble phenol resin together.
  • the thickness of an element sheet of the metal substrate may differ depending on the kind of metal and the use or the size of a seamless can, the element sheet having the thickness of 0.10 to 0.50 mm is preferably used. Particularly, with respect to the surface treatment steel sheet, it is preferable to set the thickness to 0.10 to 0.30 mm, while with respect to the light metal sheet, it is preferable to set the thickness to 0.15 to 0.40 mm.
  • Table 1 shows the compositions of resin used in respective examples and FIG. 2 shows conditions and evaluations of respective examples.
  • Polyester resin having the composition C shown in Table 1 was charged into a biaxial extruder, was extruded through T dies to form films having a thickness of 20 ⁇ m. The films were cooled by cooling rollers and the cooled film were wound to form cast films. Thereafter, the films formed in the above manner were thermally laminated to both surfaces of an aluminum alloy sheet (sheet thickness: 0.28 mm, A3004 material, chromic acid/phosphate surface treatment). The lamination was immediately followed by water cooling thus obtaining a polyester resin-coated metal sheet.
  • the temperature of the metal sheet before the lamination was set to a temperature 15 degree centigrade higher than a melting point of polyester resin and the lamination was performed by setting a temperature of lamination rolls to 150 degree centigrade and at a sheet travelling speed of 40 m/min thus producing the resin-coated metal sheet.
  • the polyester resin-coated metal sheet produced in this manner was coated with a wax-type lubricant and a disc having a diameter of 152 mm was blanked to obtain a shallow drawn cup. Then, by making the shallow drawn cup subjected to ironing working, a seamless cup was obtained.
  • cup diameter 66 mm
  • cup height 127 mm
  • This seamless cup was subjected to doming forming in accordance with a normal method. After performing the heat treatment of polyester resin at a temperature of (Tm-10) degree centigrade for three minutes, the seamless cup was cooled in atmosphere. Thereafter, post workings such as trimming working of an end peripheral portion of an opening, curved surface printing, baking, drying, neck-in working, flange working and the like were performed thus producing a seamless can having a capacity of 350 cc.
  • a seamless can was produced by a method similar to the method of the example 1 except for that this embodiment used polyester resin having the composition D shown in FIG. 1.
  • a seamless can was produced by a method similar to the method of the example 1 except for following conditions. That is, in this embodiment, polyester resin having the composition B shown in Table 1 which constitutes a surface layer and the polyester resin having the composition D shown in Table 1 which constitutes a lower layer were charged into two biaxial extruder and were extruded through a two-layer T-die thus forming a two-layered cast film, wherein a thickness of the surface layer was 5 ⁇ m and a thickness of the lower layer was 15 ⁇ m. Thereafter, a laminated material was obtained by using the cast film.
  • a seamless can was obtained by a method similar to the method of the example 3 except for that polyester resin having the composition A shown in Table 1 constitutes the surface layer and polyester resin having the composition C shown in Table 1 constitutes the lower layer.
  • the polyester resin-coated metal sheet produced in this manner was coated with a wax-type lubricant and a disc having a diameter of 166 mm was blanked to obtain a shallow drawn cup. Then, by making the shallow drawn cup subjected to thinning drawing working based on elongation, a seamless cup was obtained.
  • cup diameter 66 mm
  • cup height 128 mm
  • This seamless cup was formed into a seamless can using a method similar to that of the example 1.
  • Polyester resin having the composition F shown in Table 1 was simultaneously extruded from an extruder having a diameter of ⁇ 65 mm and coated onto both inner and outer surfaces of an aluminum alloy sheet (sheet thickness 0.28 mm, A3004 material, chroming/phosphating surface treatment) which was heated to 250 degree centigrade such that inner-side and outer-side films respectively have a thickness of 20 ⁇ m. Thereafter, the cooling was performed to produce a polyester resin-coated metal sheet.
  • a seamless can was produced in a manner similar to that of the example 6 except for that this example used polyester resin having the composition G shown in Table 1.
  • a seamless can was produced by a method similar to the method of the example 6 except for following conditions. That is, in this example, polyester resin having the composition A shown in Table 1 which constitutes a surface layer and the polyester resin having the composition F shown in Table 1 which constitutes a lower layer were simultaneously extruded and coated onto the aluminum alloy sheet through a biaxial extruder and a two-layer T-die thus forming a two-layered cast film, wherein a thickness of the surface layer was 5 ⁇ m and a thickness of the lower layer was 15 ⁇ m.
  • a seamless can was obtained by a method similar to the method of the example 8 except for that polyester resin having the composition D shown in Table 1 constitutes the surface layer and polyester resin having the composition C shown in Table 1 constitutes the lower layer.
  • a seamless can was obtained by a method similar to the method of the example 1 except for that this comparison example 1 used polyester resin having the composition A shown in Table 2 and the heat treatment shown in Table 1 was applied.
  • a seamless can was obtained by a method similar to the method of the example 1 except for that polyester resin having the composition B shown in Table 1 constitutes the surface layer and polyester resin having the composition D shown in Table 1 constitutes the lower layer, and the heat treatment shown in Table 2 was applied.
  • a resin-coated metal sheet was produced by a method similar to that of example 1 except for following conditions. That is, in this embodiment, a cast film using polyester resin having the composition A shown in Table 1 was laminated to a TFS steel sheet (sheet thickness: 0.18 mm, metal chromium quantity 120 mg/m 2 >chromium hydration oxide quantity: 15 mg/m 2 ).
  • a seamless can was obtained by a method similar to the method of the comparison example 3 except for that this comparison example 4 used polyester resin having the composition F shown in Table 1 and the heat treatment of the seamless cup was not performed.
  • a seamless can was obtained by a method similar to the method of the comparison example 3 except for that polyester resin having the composition E shown in Table 1 constitutes the surface layer and polyester resin having the composition B shown in Table 1 constitutes the lower layer, and the heat treatment of the seamless cup was not performed.
  • a seamless can was obtained by a method similar to the -method of the example 1 except for following conditions. That is, in this comparison example, after forming a cast film using polyester resin having the composition A shown in Table 1, the cast film was stretched three times respectively in the longitudinal direction as well as in the lateral direction at 100 degree centigrade. Thereafter, the cast film was subjected to the heat treatment for five seconds at 230 degree centigrade thus producing a biaxially stretched film and, then, the biaxially stretched film was subjected to the heat treatment shown in Table 2.
  • a seamless can was obtained by a method similar to the method of the example 6 except for that this comparison example 1 used polyester resin having the composition B shown in Table 1 and the heat treatment shown in Table 2 was applied.
  • a seamless can was produced by a method similar to the method of the example 6 except for following conditions. That is, in this comparison example, polyester resin having the composition E shown in Table 1 which constitutes a surface layer and the polyester resin having the composition D shown in Table 1 which constitutes a lower layer were simultaneously extruded and coated through a biaxial extruder and a two-layer T-die to form a two-layered film and the two-layered film was subjected to the heat treatment shown in Table 2.
  • a portion of the seamless can disposed at a can height of 70 to 90 mm is cut out as a sample having a square shape of 20 mm in the direction intersecting the rolling direction of the sheet material of the seamless can by 90°.
  • Metal was dissolved by hydrochloric acid of 6N so as to isolate the inner film.
  • the sample was dried under vacuum at least for 24 hours and then the density of the sample was measured at a temperature of 20 degree centigrade by a sink and float method using a density gradient tube. The measurement was performed after 1 hour elapsed from a point of time that the sample was charged into the density gradient tube.
  • a cross cut was formed on an inner film on a can barrel upper portion of the seamless can, a cellophane tape (product of Nichiban Ltd, width: 24 mm) was laminated, and the cellophane tape was peeled off.
  • the evaluation was performed by observing with naked eyes the peeled-off state of the polyester resin coating after peeling off the cellophane tape.
  • a sample having a square shape of 3 cm ⁇ 3 cm was cut out from an inner surface of the can barrel upper portion of the seamless can. After forming a cross cut on the sample using a cutter, the sample was immersed into a 0.1% sodium chloride aqueous solution. After holding this condition at a temperature of 50 degree centigrade for a week, the corrosion state was observed.
  • the weight is dropped in an erected form from a position 50 cm above the can-bottom-side terminal point. Thereafter, the can was subjected to a storing test at a temperature of 37 degree centigrade so that the state of the inner surface of the can after the lapse of one year was evaluated. Particularly, the corrosion of the can neck portion and the can bottom portion was observed and the result of the evaluation is shown in Table 2.
  • a sample was cut out from a portion of a can barrel portion of a seamless can positioned 70 mm above a can bottom portion of the seamless can and a free film of an inner surface resin layer was isolated by dissolving metal. Then, the sample was subjected to drying under vacuum for at least 24 hours. Thereafter, the infrared absorption spectrums which are polarized in the directions perpendicular to and parallel to the can height direction of the isolated film were measured.
  • the respective absorbances Iw( ⁇ ) and Iw( ⁇ ) at 973 cm ⁇ 1 were obtained, and then the infrared dichroic ratio R1 of the polyester resin layer at inner surface side of the can barrel portion was calculated by a following formula (1).
  • a portion of the can barrel upper portion of the seamless can was cut out and a free film was isolated by dissolving metal. Then, the free film was subjected to drying under vacuum at least for 24 hours. Thereafter, the density of the sample was measured and the degree of the crystallization of a resin film was calculated by a density method and the calculated result was indicated.
  • the resin-coated seamless can by performing the control such that the density of the polyester resin layer of the can inner surface side becomes equal to or more than 1.36 or by performing the control such that the infrared dichroic ratio (R1) of the polyester resin layer of the inner surface of the can barrel portion becomes equal to or more than 1.1, it is possible to produce the resin-coated seamless can having the excellent corrosion resistance, the excellent shock resistance and the excellent flavor resistance.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Rigid Containers With Two Or More Constituent Elements (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
US10/178,790 2001-06-25 2002-06-25 Resin-coated seamless can Abandoned US20030039778A1 (en)

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US20090011162A1 (en) * 2005-02-15 2009-01-08 Toyo Seikan Kaisha, Ltd. Polyester Resin For Coating Metal Plate, Resin-Coated Metal Plate Being Coated With the Same, and Metal Can and Lid
US20090206096A1 (en) * 2005-05-17 2009-08-20 Toyo Seikan Kaisha, Ltd. Three-piece square can and method of manufacturing the same
US20100021749A1 (en) * 2007-03-27 2010-01-28 Toyo Seikan Kaisha, Ltd. Polyester resin for covering metal sheets and method of producing the same
US20120018341A1 (en) * 2009-04-08 2012-01-26 Toyo Seikan Kaisha, Ltd. Resin-coated metal sheet and seamless can made therefrom
US20160145462A1 (en) * 2013-07-22 2016-05-26 Toyo Seikan Group Holdings, Ltd. Organic-resin-coated metal sheet, process for producing same, metallic can obtained by processing said organic-resin-coated metal sheet, and can lid
US10399303B2 (en) * 2014-12-12 2019-09-03 Jfe Steel Corporation Resin-coated metal sheet for can lids

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DK1669189T3 (da) * 2003-09-08 2010-01-18 Toyo Seikan Kaisha Ltd Harpikscoatet metalplade og trukket dåse, som anvender samme
CN101031416A (zh) * 2004-09-30 2007-09-05 东洋钢钣株式会社 多层树脂膜及多层树脂膜的制造方法
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WO2007013657A1 (ja) 2005-07-28 2007-02-01 Jfe Steel Corporation 樹脂被覆金属板
JP2011227940A (ja) * 2010-04-15 2011-11-10 Hoya Corp ピックアップ装置用のレンズ及び光ディスクドライブ用のピックアップ装置
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GB2511559B (en) 2013-03-07 2018-11-14 Mondelez Uk R&D Ltd Improved Packaging and Method of Forming Packaging
GB2511560B (en) 2013-03-07 2018-11-14 Mondelez Uk R&D Ltd Improved Packaging and Method of Forming Packaging
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US20090011162A1 (en) * 2005-02-15 2009-01-08 Toyo Seikan Kaisha, Ltd. Polyester Resin For Coating Metal Plate, Resin-Coated Metal Plate Being Coated With the Same, and Metal Can and Lid
US9233522B2 (en) * 2005-02-15 2016-01-12 Toyo Seikan Kaisha, Ltd. Polyester resin for coating metal plate, resin-coated metal plate being coated with the same, and metal can and lid
US20090206096A1 (en) * 2005-05-17 2009-08-20 Toyo Seikan Kaisha, Ltd. Three-piece square can and method of manufacturing the same
US20100021749A1 (en) * 2007-03-27 2010-01-28 Toyo Seikan Kaisha, Ltd. Polyester resin for covering metal sheets and method of producing the same
US20120018341A1 (en) * 2009-04-08 2012-01-26 Toyo Seikan Kaisha, Ltd. Resin-coated metal sheet and seamless can made therefrom
US8465815B2 (en) * 2009-04-08 2013-06-18 Toyo Seikan Kaisha, Ltd. Resin-coated metal sheet and seamless can made therefrom
US20160145462A1 (en) * 2013-07-22 2016-05-26 Toyo Seikan Group Holdings, Ltd. Organic-resin-coated metal sheet, process for producing same, metallic can obtained by processing said organic-resin-coated metal sheet, and can lid
US10155880B2 (en) * 2013-07-22 2018-12-18 Toyo Seikan Group Holdings Co., Ltd. Organic-resin-coated metal sheet, process for producing same, metallic can obtained by processing said organic-resin-coated metal sheet, and can lid
US10399303B2 (en) * 2014-12-12 2019-09-03 Jfe Steel Corporation Resin-coated metal sheet for can lids

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US8268422B2 (en) 2012-09-18
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EP1270201A3 (de) 2003-02-05
KR20030004047A (ko) 2003-01-14
DE60227882D1 (de) 2008-09-11
TWI235128B (en) 2005-07-01
AU785244B2 (en) 2006-11-30
US20080241448A1 (en) 2008-10-02
EP1270201B1 (de) 2008-07-30

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