WO2000058087A1 - Tole de metal enduite de resine de polyester, et boite de conserve utilisant cette tole - Google Patents

Tole de metal enduite de resine de polyester, et boite de conserve utilisant cette tole Download PDF

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Publication number
WO2000058087A1
WO2000058087A1 PCT/JP2000/001631 JP0001631W WO0058087A1 WO 2000058087 A1 WO2000058087 A1 WO 2000058087A1 JP 0001631 W JP0001631 W JP 0001631W WO 0058087 A1 WO0058087 A1 WO 0058087A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyester resin
metal plate
resin
crystallization time
coated
Prior art date
Application number
PCT/JP2000/001631
Other languages
English (en)
Japanese (ja)
Inventor
Lianchun Hu
Tomomasa Maita
Satoshi Takahashi
Hiroshi Kurisu
Original Assignee
Toyo Kohan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Kohan Co., Ltd. filed Critical Toyo Kohan Co., Ltd.
Priority to JP2000607819A priority Critical patent/JP4319358B2/ja
Priority to AU31934/00A priority patent/AU3193400A/en
Publication of WO2000058087A1 publication Critical patent/WO2000058087A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • 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
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
    • B05D2701/10—Coatings being able to withstand changes in the shape of the substrate or to withstand welding withstanding draw and redraw process, punching

Definitions

  • Polyester resin-coated metal plate and can using the same
  • the present invention relates to a polyester resin-coated metal plate and a can using the same. More specifically, it is made of a polyester resin-coated metal plate that excels in moldability, corrosion resistance, and flavor (invariant flavor) of the contents, especially for beverage cans, and is subjected to deep drawing. About cans.
  • a metal plate is coated with an oriented film of polyester resin stretched in the biaxial direction, and strict forming methods such as drawing with a high drawing ratio and a high reduction rate of the side wall of the can are used.
  • Cans made with are mainly used for beverage cans.
  • the resin film coated on the surface of the metal plate cannot completely cope with processing with large deformation, and micro cracks are generated in the film, resulting in corrosion resistance. May deteriorate or the film may break during processing, resulting in a broken body, making it impossible to make cans.Furthermore, it is extremely difficult to reduce the cost of cans by increasing the drawing ratio and reducing the thickness. .
  • the moldability will improve, but the crystallinity of the resin will decrease, and the permeation resistance of the resin film to water and oxygen will decrease.
  • the corrosion resistance and the flavor of the contents become poor.
  • the present invention provides a polyester resin-coated metal plate which does not crack or break even when subjected to a severe forming process such as a thinning drawing process, and is excellent in heat resistance and corrosion resistance, and using the same.
  • An object is to provide a can excellent in the flavor of the contents. Disclosure of the invention
  • Boriesuteru resin-coated metal sheet according to claim 1, characterized in that specific viscosity in one side at least of the metal plate is 0.6 to 1.4
  • the half-crystallization time of the polyester resin measured using a differential scanning calorimeter is preferably 50 seconds or more.
  • the half-crystallization time of the upper layer be shorter than the half-crystallization time of the lower layer.
  • polyester resin is non-oriented.
  • the metal plate is desirably any one of a tin-plated steel plate, tin-free steel, and an aluminum alloy plate.
  • the can of claim 7 is characterized by using the polyester resin-coated metal plate according to any one of claims 1 to 6. BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 is a diagram showing an example of a half-crystallization time of a polyester resin.
  • FIG. 2 is a schematic diagram of an apparatus for manufacturing a polyester resin-coated metal plate. BEST MODE FOR CARRYING OUT THE INVENTION
  • the present invention relates to a single-layer polyester resin having an intrinsic viscosity of 0.6 to 1.4 and a half-crystallization time of 50 seconds or more, or an upper layer having a half-crystallization time of less than 80 seconds and a lower layer having a half-crystallization time of less than 80 seconds. Aging time is 50 seconds or more, and the intrinsic viscosity of both layers is 0.6 to 1.4.
  • polyester resin applied to the present invention will be described.
  • a polyester resin having ester units such as ethylene terephthalate, ethylene isophthalate, butylene terephthalate, and butylene isophthalate is preferable, and at least one ester unit selected from these is preferable.
  • the polyester is a polyester.
  • each ester unit may be copolymerized, or two or more homopolymers or copolymers of each ester unit may be blended and used.
  • the acid component of the ester unit includes naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, etc.
  • the resin's intrinsic viscosity is increased and the resin is reinforced to prevent the resin from being chipped or flawed even after application, and to prevent cracking, cracking, and further peeling. There is a need.
  • the intrinsic viscosity of the above polyester resin is preferably in the range of 0.6 to 1.4, and more preferably in the range of 0.8 to 1.2.
  • the half-crystallization time of the polyester resin measured using a differential scanning calorimeter is preferably 50 seconds or more.
  • the half crystallization time in the present invention is defined as follows.
  • a certain weight of the polyester resin peeled off from the polyester resin-coated metal plate was heated at a rate of 90 ° C / min to a temperature above the melting temperature of the polyester resin. Heat to 3 ° C, melt and hold for 3 minutes, then rapidly cool to 30 ° C at a cooling rate of 200 ° C / min to make the resin amorphous.
  • the amorphous resin obtained in this manner was again subjected to DSC at a heating rate of 90 ° C / min using DSC.
  • the above polyester resin is a resin having two layers, that is, the upper layer is a polyester resin having a half-crystallization time of less than 80 seconds, and the lower layer is a polyester resin having a half-crystallization time of 50 seconds or more.
  • Some two layers of polyester resin may be coated on the metal plate.
  • the lower polyester resin is required to have a low V 5 half crystallization time of 50% in order to secure adhesion to the metal plate, particularly during processing. It is preferable to use a polyester resin having a duration of at least seconds.
  • the polyester resin in the upper layer is a polyester resin with a high crystallinity half-crystallization time of less than 80 seconds in order to improve the permeation resistance of the contents to ensure corrosion resistance and at the same time to ensure good flavor. It is preferable that the half-crystallization time of the upper layer be shorter than the half-crystallization time of the lower layer in order to more effectively use the two-layer polyester resin.
  • the polyester resin used in the present invention can be subjected to severe processing such as thinning drawing without cracking, cracking, peeling, etc. of the resin. Used in the state of orientation.
  • the thickness of the polyester resin when coated on a metal plate is preferably 5 to 60 ⁇ m, more preferably 10 to 40 ⁇ when coated with a single layer. New If the thickness is less than 5 ⁇ m, the work of coating the resin on the metal plate becomes extremely difficult, and the resin layer after thinning drawing is apt to have defects, and the penetration resistance is not sufficient. Absent. On the other hand, if the thickness is increased, the permeation resistance is sufficient, but increasing the thickness to 60 / m or more is economically disadvantageous.
  • f resin is 2 to 57 // m and the thickness of the lower layer resin is 3 to 58 m. If the thickness of the upper layer resin is extremely thin, the permeation resistance and flavor properties may not be sufficient depending on the content.On the other hand, if the thickness of the lower layer resin is extremely thin, the processing adhesion may be poor. Will be insufficient.
  • Lubricants such as stabilizers, antioxidants, and silica may be included in the above resins as long as the required properties are not impaired.
  • the metal plate serving as the substrate of the polyester resin-coated metal plate of the present invention includes various types of tinplate and electrolytic chromic acid-treated steel plate (Tinfree steel, hereinafter referred to as TFS) widely used as a material for ordinary cans.
  • TFS electrolytic chromic acid-treated steel plate
  • Surface-treated steel sheets and aluminum alloy sheets can be used. 1 0 ⁇ 2 0 O mg / m 2 as a surface-treated steel sheet, of a lower layer comprising a coating of metal chromium, the upper layer comprising a coating of hydrated chromium oxides 1 ⁇ 3 O mg / m 2 in terms of chromium
  • a two-layer film consisting of Infra-free steel is preferred, has sufficient adhesion to the polyester resin of the present invention, and also has corrosion resistance.
  • the steel sheet serving as the substrate is preferably a low-carbon cold-rolled steel sheet generally used as a material for cans.
  • the thickness of the steel sheet is preferably 0.1 to 0.32 mm.
  • the aluminum alloy plate 3 000 system JIS or preferably of 50 00 based, by electrolytic chromic acid treatment on the surface, and a lower layer consisting of 0 ⁇ 20 0mgZm iC 2 of coating weight of metallic chromium, chromium terms 1 to 3 OmgZm or a two-layer film comprising an upper layer and consisting of 2 skins film of hydrated chromium oxide as to form, or 1 to 30 mg / m 2 of chromium Ingredients in terms of chromium with phosphate chromate treatment If, Le Shi preferred those phosphorus component in the phosphate conversion 0 ⁇ 3 Omg / m 2 is attached.
  • the thickness of the aluminum alloy plate is preferably 0.15 to 0.4 mm.
  • any of the known film laminating method and extrusion laminating method can be applied.
  • the resin pellet When coating by the film lamination method, the resin pellet is heated and melted at a temperature 20 to 40 ° C higher than the melting temperature of the resin, cast on a cast roll cooled from a T-die, and wound on a coiler without stretching. A non-oriented resin film is produced.
  • the long 0-long strip-shaped metal plate is heated at a temperature 20 to 40 ° C higher than the melting temperature of the resin while being unwound from the uncoiler, and brought into contact with the heated metal plate while unwound the non-oriented resin film. Immediately after being sandwiched between a pair of laminating rolls and pressed, immediately cooled in water to prevent crystallization.
  • the resin pellet was heated and melted at a temperature 20 to 40 ° C higher than the melting temperature of the resin, and cast directly from a T-die on a long strip-shaped metal plate unwound from the uncoiler. Then, immediately cool in water to prevent crystallization.
  • the laminate may be formed by interposing an adhesive between the polyester resin and the metal plate. This laminating method is applied when tinplate or the like that cannot raise the temperature of the metal plate so much is used because the plating layer of the metal plate is dissolved in the film laminating method.
  • the kind of the adhesive is not particularly limited, but an adhesive such as an epoxy-based adhesive, an epoxy / urea-based adhesive, and a urethane-based adhesive can be suitably used.
  • the polyester resin-coated metal plate of the present invention may be such that one side of the metal plate is coated with the polyester resin of the present invention as described above, and the other side is not coated with the resin,
  • a resin other than the present invention for example, a biaxially oriented polyester resin film 10, a non-oriented polyester resin other than the present invention, a polyamide polyolefin other than polyester, or a resin obtained by coloring these resins simultaneously or on one side You may coat them one by one. Further, various resin coatings may be applied.
  • a copolyester resin consisting of 0 melting temperature: 229 ° C
  • white resin melting temperature
  • PET in Table 1 is polyethylene terephthalate
  • PETI is ethylene terephthalate and ethyleneisophthalate copolymerized polyester resin.
  • the numerical values described after the resin composition in Table 1 indicate mol% of isophthalic acid.
  • Sample No. 8 indicates that the resin composition is a blend of PETI—10 mol% (67 wt%) and PET 1-25 mol 0 / o (33 wt%).
  • the resin composition of the lower layer was PETI—10 mol. /. Indicates that the blend of (6 7 wt%) and PETI- 25 mole 0/0 (3 3 wt% ).
  • Chromium hydrated oxide amount (Chromium and 8 mg / m '
  • polyester resin is laminated on one side and white resin is laminated on the other side.
  • the polyester resin-coated metal sheet obtained as described above was formed into a bottomed cylindrical can by using a thinning drawing method as described below.
  • a drawn can having a can bottom diameter of 10 Omm was made so that the white resin-coated surface was the outer surface of the can.
  • a redrawing can with a bottom diameter of 80 mm was performed by redrawing. The redrawn cans were subjected to stretching and ironing at the same time as the combined processing to form drawn ironed cans with a can bottom diameter of 65 mm.
  • the distance between the redrawing part and the ironing part at the upper end of the can is 20 mm
  • the shoulder radius of the redrawing die is 1.5
  • the clearance was 1.0 times the plate thickness
  • the clearance at the ironed portion was 50% of the original plate thickness.
  • the upper portion of the can was trimmed by a known method, and a neck-in process and a flange process were performed.
  • the non-oriented film was embedded in epoxy-based embedding resin, sliced to a thickness of 5 ⁇ m, and the cross section was measured by microscopic observation.
  • the can formed by the thinning drawing method was visually observed, and the formability was evaluated based on the following criteria.
  • Table 2 shows the results of these evaluations.
  • the polyester resin-coated metal sheets of the present invention are all excellent in moldability and exhibit good corrosion resistance and flavor, but the upper layer is a polyester resin having high crystallinity, and the lower layer is low crystalline.
  • the metal plate By coating the metal plate with two layers of resin made of a conductive polyester resin, corrosion resistance and flavor characteristics are further improved.
  • the present invention relates to a single-layer polyester resin having an intrinsic viscosity of 0.6 to 1.4 and a half-crystallization time of 50 seconds or more, or a half-crystallization time of an upper layer polyester resin of less than 80 seconds j0.
  • the can j lj- using the polyester resin-coated metal plate of the present invention is excellent in the flavor of the contents.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une tôle de létal enduite de polyester faite d'une tôle de métal recouverte, sur l'une au moins de ses faces, soit d'une unique couche de résine de polyester présentant une viscosité intrinsèque de 0,6 à 1,4 pour une demi-période de cristallisation d'au moins 50 secondes, soit de deux couches de résine de polyester, auquel cas la couche supérieure de résine de polyester présente une demi-période de cristallisation n'excédant pas 80 secondes, la couche inférieure de résine de polyester présentant une demi-période de cristallisation d'au moins 50 secondes, la viscosité intrinsèque des deux couches étant de 0,6 à 1,4. L'invention concerne également une boîte de conserve faite dans cette tôle de métal. Cette tôle de métal enduite d'un polyester est exempte de craquelures ou de fissures, même après des opérations lourdes de formage ou de traitement telles que l'amincissement des parois ou l'emboutissage profond. En outre, elle se prête particulièrement bien au traitement et présente une bonne résistance à la corrosion. Elle convient particulièrement à la préservation des propriétés organoleptiques des produits qu'elle sert à contenir.
PCT/JP2000/001631 1999-03-25 2000-03-17 Tole de metal enduite de resine de polyester, et boite de conserve utilisant cette tole WO2000058087A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2000607819A JP4319358B2 (ja) 1999-03-25 2000-03-17 ポリエステル樹脂被覆金属板、およびそれを用いた缶
AU31934/00A AU3193400A (en) 1999-03-25 2000-03-17 Metal plate coated with polyester resin, and can using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/81562 1999-03-25
JP8156299 1999-03-25

Publications (1)

Publication Number Publication Date
WO2000058087A1 true WO2000058087A1 (fr) 2000-10-05

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PCT/JP2000/001631 WO2000058087A1 (fr) 1999-03-25 2000-03-17 Tole de metal enduite de resine de polyester, et boite de conserve utilisant cette tole

Country Status (3)

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JP (1) JP4319358B2 (fr)
AU (1) AU3193400A (fr)
WO (1) WO2000058087A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003063519A (ja) * 2001-08-23 2003-03-05 Toyo Seikan Kaisha Ltd 樹脂被覆シームレス缶
WO2005053947A1 (fr) * 2003-12-01 2005-06-16 Jfe Steel Corporation Feuille metallique laminee pour couvercle de boite presentant une excellente apparence apres sterilisation en autoclave
EP1688187A1 (fr) * 2005-02-02 2006-08-09 Toyo Kohan Co., Ltd. Tôle de métal revêtue de résine polyester, et boîte de conserve utilisant cette tôle
EP1688188A1 (fr) * 2005-02-02 2006-08-09 Toyo Kohan Co., Ltd. Tôle de métal revêtue de résine polyester, et boîte de conserve utilisant cette tôle
WO2010137550A1 (fr) * 2009-05-28 2010-12-02 東洋製罐株式会社 Boîte en acier embouti et étiré, et son procédé de fabrication
WO2011010508A1 (fr) * 2009-07-22 2011-01-27 東洋製罐株式会社 Boîte en aluminium emboutie et étirée et procédé de production
US11433647B2 (en) 2015-06-16 2022-09-06 Toyo Kohan Co., Ltd. Polyester resin-coated metal sheet and container using same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160755A (ja) * 1997-08-12 1999-03-05 Mitsubishi Kagaku Polyester Film Kk 金属缶被覆用ポリエステルフィルム
JPH11209483A (ja) * 1998-01-23 1999-08-03 Teijin Ltd 金属板貼合せ成形加工用白色ポリエステルフィルム

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1160755A (ja) * 1997-08-12 1999-03-05 Mitsubishi Kagaku Polyester Film Kk 金属缶被覆用ポリエステルフィルム
JPH11209483A (ja) * 1998-01-23 1999-08-03 Teijin Ltd 金属板貼合せ成形加工用白色ポリエステルフィルム

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003063519A (ja) * 2001-08-23 2003-03-05 Toyo Seikan Kaisha Ltd 樹脂被覆シームレス缶
WO2005053947A1 (fr) * 2003-12-01 2005-06-16 Jfe Steel Corporation Feuille metallique laminee pour couvercle de boite presentant une excellente apparence apres sterilisation en autoclave
JP2005161621A (ja) * 2003-12-01 2005-06-23 Jfe Steel Kk レトルト後の外観に優れた缶蓋用ラミネート金属板
EP1688187A1 (fr) * 2005-02-02 2006-08-09 Toyo Kohan Co., Ltd. Tôle de métal revêtue de résine polyester, et boîte de conserve utilisant cette tôle
EP1688188A1 (fr) * 2005-02-02 2006-08-09 Toyo Kohan Co., Ltd. Tôle de métal revêtue de résine polyester, et boîte de conserve utilisant cette tôle
JP2010274960A (ja) * 2009-05-28 2010-12-09 Toyo Seikan Kaisha Ltd スチール製絞りしごき缶及びその製造方法
WO2010137550A1 (fr) * 2009-05-28 2010-12-02 東洋製罐株式会社 Boîte en acier embouti et étiré, et son procédé de fabrication
CN102448840A (zh) * 2009-05-28 2012-05-09 东洋制罐株式会社 拉深减薄钢罐及其生产方法
US8968850B2 (en) 2009-05-28 2015-03-03 Toyo Seikan Kaisha, Ltd. Draw-ironed steel can and method of producing the same
WO2011010508A1 (fr) * 2009-07-22 2011-01-27 東洋製罐株式会社 Boîte en aluminium emboutie et étirée et procédé de production
JP2011025935A (ja) * 2009-07-22 2011-02-10 Toyo Seikan Kaisha Ltd アルミニウム製絞りしごき缶及びその製造方法
CN102470952A (zh) * 2009-07-22 2012-05-23 东洋制罐株式会社 拉深减薄的铝罐及其生产方法
US8647729B2 (en) 2009-07-22 2014-02-11 Toyo Seikan Kaisha, Ltd. Draw-ironed aluminum can and method of producing the same
US11433647B2 (en) 2015-06-16 2022-09-06 Toyo Kohan Co., Ltd. Polyester resin-coated metal sheet and container using same

Also Published As

Publication number Publication date
AU3193400A (en) 2000-10-16
JP4319358B2 (ja) 2009-08-26

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