US20060210814A1 - Laminated metal sheet and process for producing the same - Google Patents

Laminated metal sheet and process for producing the same Download PDF

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Publication number
US20060210814A1
US20060210814A1 US10/568,652 US56865206A US2006210814A1 US 20060210814 A1 US20060210814 A1 US 20060210814A1 US 56865206 A US56865206 A US 56865206A US 2006210814 A1 US2006210814 A1 US 2006210814A1
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Prior art keywords
film
melting point
metal sheet
low melting
laminated metal
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English (en)
Inventor
Hayato Kazeoka
Sotoji Ohsasa
Akihiro Murata
Tadaaki Ochiai
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Nippon Steel Corp
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Individual
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Priority claimed from JP2003207664A external-priority patent/JP4537673B2/ja
Priority claimed from JP2003343969A external-priority patent/JP4183126B2/ja
Application filed by Individual filed Critical Individual
Assigned to NIPPON STEEL CORPORATION reassignment NIPPON STEEL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAZEOKA, HAYATO, MURATA, AKIHIRO, OCHIAI, TADAAKI, OHSASA, SOTOJI
Publication of US20060210814A1 publication Critical patent/US20060210814A1/en
Priority to US12/317,201 priority Critical patent/US8551281B2/en
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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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203—One or more of the layers being plastic
    • B32B37/206—Laminating a continuous layer between two continuous plastic layers
    • 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
    • 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
    • B32B15/085—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 polyolefins
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • B32B5/142—Variation across the area of the layer
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/66—Cans, tins
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • the present invention relates to a laminated metal sheet used as a material for food cans and other containers and comprised of a metal sheet laminated on the front and back with two types of resins with different melting points and a method of production of the same.
  • metal sheets covered on their surfaces with a polyester, polyolefin, or other thermoplastic resin are being made much use of.
  • the metal sheet used is generally steel sheet or aluminum sheet.
  • polyester-based resins are generally superior in corrosion resistance, flaw resistance, and printability and can be used for both the inner surface and outer surface of cans in some cases, but when the content is alkaline, the resin is insufficient in durability.
  • the meat releasability is poor.
  • two-sided laminated metal sheets covered with different types of resin at the can inside surface side and the can outer surface side are being used.
  • a relatively hard polyester-based resin film is preferably used, while as the can inside surface side film, a lower melting point, excellent meat releasability and alkali durability, relatively soft polyolefin-based resin film is preferably used.
  • Metal sheet laminated with different films on its two surfaces is disclosed in Japanese Patent Publication (A) No. 63-231926, Japanese National Publication (A) No. 2-501644, and Japanese Patent Publication (A) No. 2002-120324. Note that the terms “high melting point film” and “low melting point film” used in the present description do not mean films with melting points of absolute values.
  • a relatively high melting point side film is called a “high melting point film”, while a relatively low melting point side film is called a “low melting point film”.
  • a laminated metal sheet is produced by the method of superposing a heated metal sheet and resin films and using lamination rolls to apply pressure to bond them (heat lamination method).
  • the temperature of a film surface contacting the metal sheet has to be at least its melting start point Tsm (normally a temperature about 0 to 30° C. lower than the melting point), more preferably at least the melting point MP, but on the other hand if the temperature of a film surface contacting a lamination roll becomes the melting start point or more, the film will stick to the lamination roll making production impossible.
  • the temperature of the metal sheet at the lamination part has to be strictly controlled in relation with the film melting points, but when using a polyester-based resin film as the high melting point film and using a polyolefin-based resin film as the low melting point film, since the melting points MP of the two greatly differ (for example, polyethylene terephthalate (polyester-based) has a melting point of 265° C., while polypropylene (polyolefin-based) has one of 168° C.), there is the problem that if setting the temperature of the metal sheet to match with one of the films, the other film will not bond well.
  • polyethylene terephthalate polyethylene terephthalate
  • polypropylene polyolefin-based
  • Japanese Patent Publication (A) No. 63-231926 the method of first laminating the high melting point resin film, then laminating the low melting point resin film in a later step where the temperature of the metal sheet falls, that is, a two-step lamination method, and, as shown in Japan National Publication (A) No. 2-501644, the method of reheating after the lamination step by the press-bonding of the lamination rolls so as to melt-bond the resins have been proposed, but both of these have the problems of swelling capital costs. Further, Japanese Patent Publication (A) No.
  • 2002-120324 proposes a simultaneous lamination method matching the temperature of the metal sheet with the low melting point resin film, but it is believed that a low melting point resin for bonding purposes is required at the metal sheet side of the high melting point resin film, so again the cost rises.
  • the present invention solves the above problems of the prior art and provides a laminated metal sheet enabling simultaneous lamination of two types of film with different melting points, without sticking on the lamination rolls, on the two surfaces of a metal sheet and a method of production of the same. Further, the present invention provides more inexpensively a two-sided laminated metal sheet free from the low melting point resin film whitening even when working the sheet to produce a food can etc.
  • the present invention has as its gist the following.
  • MP 1 melting point of high melting point film (° C.)
  • a laminated metal sheet as set forth in (1) characterized in that said high melting point film is comprised of a polyester-based resin and said low melting point film is comprised of a polyolefin-based resin.
  • polyester-based resin is selected from polyethylene terephthalate, a polyethylene terephthalate/isophthalate copolymer, polyethylene naphthalate, a polyethylene terephthalate/naphthalate copolymer, a mixed resin of polybutylene terephthalate and polyethylene terephthalate, a mixed resin of polybutylene terephthalate and a polyethylene terephthalate/isophthalate copolymer, and further one of these resins including a pigment or dye.
  • a laminated metal sheet as set forth in (2) characterized in that said olefin-based resin is selected from a polypropylene, polyethylene, a polypropylene/polyethylene random copolymer, or these resins including a pigment or dye.
  • a laminated metal sheet as set forth in (1) characterized in that a difference ⁇ Hz between a haze value Hz 2 of a low melting point film after bending a sheet of a thickness of 1 mm by 180 degrees across said high melting point film side and a haze value Hz 1 of the low melting point film before bending is made not more than 20%.
  • a laminated metal sheet as set forth in (1) characterized in that, among the two types of film including said high melting point film and low melting point film, when the melting points inside the films differ according to the position in the thickness direction, the lower surface melting point of the one film at the side contacting the roll is designated as MP 2 and the film melting point of the other film at the metal sheet side is designated as MP 1 for calculation and lamination.
  • a laminated metal sheet as set forth in (8) characterized in that the sheet running speed V defined in (1) is made 1 to 3.5 m/s for lamination.
  • FIG. 1 is an enlarged sectional view of a two-sided laminated metal sheet of the present invention.
  • FIG. 2 is an explanatory view of a process of production of a two-sided laminated metal sheet.
  • FIG. 3 is a view of the temperature profiles immediately before the rolls separate from the films in the case of laminating same melting point films on the two sides of a metal sheet.
  • FIG. 4 is a graph of a heat conduction analysis model.
  • FIG. 5 is a graph of temperature gradients inside the two types of film.
  • FIG. 6 is a graph of a method for finding a thickness by which a film will not stick to the rolls.
  • FIG. 7 is a view of the temperature profiles at the lamination roll exit side in the present invention.
  • FIG. 8 is an explanatory view of bending by 180 degrees.
  • FIG. 9 is a perspective view of an easy peel EOE.
  • FIG. 1 is an enlarged sectional view of a two-sided laminated metal sheet of the present invention, wherein 3 indicates a steel sheet, aluminum sheet, or other metal sheet, 1 a high melting point film laminated at one side of this metal sheet 3 , and 2 a low melting point film laminated at the other side of this metal sheet 3 .
  • FIG. 2 is an explanatory view of a process of production of a two-sided laminated metal sheet according to the present invention.
  • 10 indicates a pair of left and right lamination rolls.
  • a high melting point side film 1 and a low melting point side film 2 are superposed over the two sides of the metal sheet 3 and press bonded by the lamination rolls 10 .
  • the metal sheet 3 is for example a steel sheet. In the case of use as a material for a container, the metal sheet 3 has a thickness of 0.1 to 0.5 mm or so in usual cases.
  • the high melting point side film 1 is, for example, a relatively hard, superior printability, flaw resistance, retort bondability, etc.
  • polyester-based resin while the low melting point side film 2 is, for example, a superior corrosion resistance, workability, meat releasability, retort bondability, etc. polyolefin-based resin.
  • A indicates a point immediately before the metal sheet 3 and films contact
  • B indicates a point immediately before the films separate from the lamination rolls 10 .
  • the metal sheet 3 is heated in advance to a temperature at least the melting start point of the high melting point side film 1 , preferably the melting point+50° C. or less, for example, 270° C.
  • a temperature at least the melting start point of the high melting point side film 1 preferably the melting point+50° C. or less, for example, 270° C.
  • FIG. 3 schematically shows, for explanatory purposes, the temperature profiles inside the metal sheet and films immediately before the rolls separate from the films in the case where the same melting point films are bonded to the two sides of the metal sheet 3 .
  • each film has at thickness determined by the reason that for example the lower limit of film formation is 10 ⁇ m or that for corrosion resistance to be maintained, 20 ⁇ m or more is necessary.
  • the conditions under which a film will not stick to a roll are conditions where, while the roll and film are in contact, the temperature at the point C of the film thickness position is less than the melting start point Tsm 1 . This can be achieved by selecting the lamination conditions.
  • the high melting point side film generally has a thickness of 20 to 30 ⁇ m or so, but greater thicknesses can be obtained for other applications.
  • the temperature of the metal sheet when contacting the films normally becomes higher than the melting start point Tsm 1 of the films, but at the point of time when the rolls separate from the films, as shown in FIG. 3 , it becomes lower than the melting start point Tsm 1 of the films. This is because heat is removed through the film to the roll side.
  • This condition becomes a required condition of the roll inlet side temperature for bonding the high melting point film to a metal sheet when laminating two types of film with different melting points.
  • ⁇ is determined by the heat removal conditions at the time of lamination and specifically is determined by adjusting the lamination rolls in surface temperature or pressing force. ⁇ 1. In general, 0.75 ⁇ 1 can be adjusted to.
  • the low melting point side film is adjusted in thickness d 2 to specifically make d 2 ⁇ k ( ⁇ MP ⁇ T)/V and thereby solve this problem.
  • k ⁇ 2 ⁇ L Cp 2 ⁇ ⁇
  • a one-dimensional heat conduction analysis model of the inside of a film having an abscissa x indicating the film thickness and an ordinate indicating the temperature T is prepared.
  • the temperature of the side of the film contacting the roll is less than the melting start point Tsm 1 , it is assumed that the film will not stick to the roll.
  • the distance d not sticking to the roll becomes the necessary film thickness.
  • d 2 is found from d 2 ⁇ k( ⁇ MP ⁇ T)/V.
  • the films can be made thinner in thickness d 2 , but for the runnability of the films or the uniform heating of the metal sheet, it is not preferable that the sheet running speed V be made that high. Normally, the operation is performed at 2.5 to 3.5 m/s or so. However, depending on the facility, it is of course possible to make the value one over 3.5 m/s.
  • the metal sheet various types of metal generally used as container materials such as aluminum sheet, soft steel sheet, various types of plated steel sheet, stainless steel sheet, etc. may be used.
  • the resin forming the high melting point film 1 may in principle be any thermoplastic resin.
  • the metal sheet surface a chromate coating, give the surface of the resin contacting the steel sheet an adhesive layer having polarity, etc. in combination.
  • the resin forming the low melting point film 2 may in principle be any thermoplastic resin. Resins selected from polypropylene, polyethylene, a polypropylene/polyethylene random copolymer, or these resins including a pigment or dye are frequently used. These polyolefin-based resins are lower in melting point compared with the polyester-based resin forming the high melting point film 1 .
  • the polyethylene terephthalate resin used as the high melting point film 1 has a melting point of 265° C.
  • the polypropylene resin used as the low melting point film 2 has a melting point of 168° C.
  • the two-sided laminated metal sheet of the present invention is one in which the low melting point film 2 is adjusted in thickness to become thicker and is simultaneously laminated under relatively high temperature conditions matching the temperature conditions of the metal sheet 3 with the high melting point film 1 .
  • the laminated low melting point film 2 is heated to a considerably higher temperature than the conventional two-sided laminated metal sheet and becomes amorphous.
  • the two-sided laminated metal sheet of the present invention becomes resistant to whitening even when bending for working it into a container etc. Clarifying this point by numerical values, in the present invention, as shown in FIG. 8 , a sheet 4 having a thickness of 1 mm is bent 180 degrees to the outside across the high melting point film 1 side.
  • the whitenesses of the low melting point film 2 before and after this are defined by the haze values. That is, the bending work is 180 degree bending so that the low melting point film 2 becomes the outside.
  • the haze value is the value defined as the diffusion transmittance/total light transmittance ⁇ 100 (%) when optically measuring the haze value of the film.
  • the measurement method is prescribed in JIS-K7136.
  • the two-sided laminated metal sheet before bending and after bending is immersed in 40° C. 18% HCl to make the metal sheet 3 dissolve, the low melting point film 2 is peeled off, then a 50 mm ⁇ 50 mm sample for measurement of the haze is taken so that the bent part becomes the center, the measurement is performed three times, and the average value is taken. The measurement is performed centered at the bent part.
  • the haze value Hz 1 of the low melting point film 2 before bending is preferably not more than 60%.
  • the whitening at the time of the bending work is accompanied with the formation of microcracks, but if ⁇ Hz is made not more than 20% as shown in the following examples, this problem can be avoided. Further, if the haze value Hz 1 of the low melting point film 2 before bending is over 60%, the inner surface of the can whitens in appearance, so this is not preferable.
  • the two-sided laminated metal sheet of the present invention has a difference ⁇ Hz of the haze values of the low melting point film 2 before and after bending of not more than 20% and can be produced by the low production cost simultaneous lamination method.
  • the temperature conditions of the metal sheet 3 can be set matching with the characteristics of the high melting point film 1 , so it is possible to use for the high melting point film a biaxially stretched polyester-based resin film and laminate it in the state with that surface layer having residual crystal orientation.
  • the high melting point film 1 is usually made the outside and the low melting point film 2 the inside.
  • the easy peel EOE easy open end
  • the low melting point film 2 is used as the top side (can outer surface side). In this way, which side to make the outside of the container may be suitably determined in accordance with the application.
  • PP shows polypropylene film, but pure PP is nonpolar and cannot sufficiently be bonded by heat lamination, so one giving the metal bonding surface side a modified PP adhesive layer (melting point 166° C.) having a thickness of 4 ⁇ m and polarity is used.
  • the polyethylene film shown as PE is also nonpolar and cannot be sufficiently bonded by heat lamination in the pure state, so one giving the metal bonding surface side an ethylene acrylate copolymer resin adhesive layer (melting point 99° C.) of a thickness of 10 ⁇ m is used.
  • PET-IA*5 226 20 PE*8 112 60 2.5 257 0.778 200 2 70.4 13 Comp. Ex. 5 PET*6 265 13 PP*7 168 40 2.5 285 0.842 240 2 57.6 *EAA: ethylene acrylate copolymer
  • Comparative Example 1 is an example in which the other conditions are made the same as in Invention Example 1, but the thickness of the film 2 is made 25 ⁇ m or smaller than the 25.5 ⁇ m of the calculated value of d 2 and sticking to the lamination roll occurred. Therefore, an example in which the other conditions are made the same, but the sheet running speed of Comparative Example 1 is raised to 2.9 m/s is Invention Example 2. Due to this, the calculated value of d 2 becomes 22 ⁇ m or less than the 25 ⁇ m of the thickness of the film 2 . As a result, sticking to the lamination roll can be avoided.
  • Comparative Example 3 is an example in which ⁇ Ti is raised to 226° C. or equal to the melting point MP 1 of the film 1 .
  • the film 2 stuck to the lamination roll.
  • Invention Example 3 is an example of changing the type of the film 2 from Invention Example 1 to PE. A laminated metal sheet was produced without allowing sticking to the lamination rolls.
  • Comparative Example 4 is an example in which the conditions were made the same as in Invention Example 3 and the thickness of the film 2 was made 60 ⁇ m or thinner than the 70.4 ⁇ m of the calculated value of d 2 . Sticking of the film 2 to the lamination roll occurred.
  • Comparative Example 5 is also an example in which the thickness of the film 2 was made 40 ⁇ m or thinner than the calculated value of d 2 . Sticking of the film 2 to the lamination roll occurred. Therefore, in Invention Example 4, the other conditions were made the same as those of Comparative Example 5 and the thickness of the film 2 was made 70 ⁇ m. As a result, the film no longer stuck to the lamination roll. Even if retort sterilizing the obtained laminated metal sheet, the film 1 did not peel.
  • Invention Example 6 is an example where even if the sheet running speed was made the lower limit of 1 m/s, lamination was possible without trouble. Further, Invention Example 7 is an example in which even if the sheet running speed is made the 3.5 m/s upper limit value of the facility, lamination was possible without trouble. Invention Example 8 is an example of use of a two-layer PET film as the film 1 . This two-layer PET film is comprised of an outside of PET of a thickness of 7 ⁇ m and a melting point of 265° C. and an inside of PET-IA (*5) of a thickness of 6 ⁇ m and a melting point of 226° C.
  • Ia/Ib is the ratio of the following two peaks obtained by X-ray diffraction measurement using CuK ⁇ -rays at a two-sided laminated metal sheet at the high melting point film (polyester film) covered side.
  • Ia is the X-ray diffraction intensity of the diffraction face of the (100) face parallel to the surface of the polyester film (distance between faces about 0.34 nm), while Ib is similarly the X-ray diffraction intensity by the diffraction face of the (110) face (distance between faces about 0.39 nm).
  • Ia/Ib is 0.7 to 10 in range and shows that the crystal orientation remains without complete melting up to the surface layer.
  • the corrosion resistance after working is the result from punching a two-sided laminated metal sheet into a disk shape of a diameter of 158 mm, drawing it by a draw ratio of 1.56 so that the low melting point film becomes the inner surface to obtain a shallow drawn cup, then redrawing it by a draw ratio of 1.23 to obtain a can of a cup diameter of 82 mm and a cup height of 52 mm (DRD can), filling the inside with 2% citric acid, then storing it at 37 degrees for six months and examining the inside surface of the can for the state of corrosion.
  • PET-PBT is a mixed resin of polyethylene terephthalate and polybutylene terephthalate.
  • Two-layer PET is two-layer structure film with a surface layer of 10 ⁇ m PET (MP 265° C.) and a bottom layer of 10 ⁇ m PET-IA (MP about 150° C.).
  • PET-IA is polyethylene terephthalate/isophthalate copolymer.
  • PET is polyethylene terephthalate.
  • PP is polypropylene
  • PE is polyethylene
  • Table 3 shows examples of the present invention.
  • the two types of films of the materials shown in the table were simultaneously laminated on the two sides of steel sheets.
  • MP 1 indicates the melting point of the high melting point film
  • d 1 indicates its thickness
  • MP 2 indicates the melting point of the low melting point film
  • d 2 indicates its thickness.
  • the sheet temperature Ti indicates the metal sheet temperature at the time of lamination
  • the speed v indicates the sheet running speed at the time of lamination.
  • Hz 1 and Hz 2 were measured by the method explained above based on JIS-K7136. Further, Table 4 shows comparative examples.
  • PET-IA*5 226 20 PP *7 168 40 233 2.5 35.2 44.8 9.6 1.5 Good Very No abnor- Ex. 14 good mality Inv. PET-IA*5 226 13 PP *7 168 40 228 2.5 34.3 48.9 14.6 3.2 Good Very No abnor- Ex. 15 good mality Inv. PET-PBT*3 214 12 PP *7 168 40 216 2.5 32.6 50.2 17.6 3.9 Good Good No abnor- Ex. 16 mality Inv. PET-IA*5 226 20 PE*8 112 80 257 2.5 48.5 50.8 2.3 0.7 Good Very No abnor- Ex. 17 good mality Inv.
  • PET*4 150 corrosion Comp. 2-layer to 20 PP *7 168 20 150 2.5 13.8 49.6 35.8 12.5 Poor Poor Large Ex. 13 PET*4 150 corrosion Comp. 2-layer to 20 PP *7 168 15 150 2.5 6.2 38.9 32.7 12.3 Poor Poor Large Ex. 14 PET*4 150 corrosion Comp. PET-IA*5 226 13 PE*8 112 90 228 2.5 57.3 78.6 21.3 3.1 Poor Poor Small Ex. 15 corrosion
  • Ia/Ib is the ratio of the following two peaks obtained by X-ray diffraction measurement using CuK ⁇ -rays at a two-sided laminated metal sheet at the high melting point film (polyester film) covered side.
  • Ia is the X-ray diffraction intensity by the diffraction face of the (100) face parallel to the surface of the polyester film (distance between faces about 0.34 nm), while Ib is similarly the X-ray diffraction intensity by the diffraction face of the (110) face (distance between faces about 0.39 nm).
  • Ia/Ib is 0.7 to 10 in range and shows that the crystal orientation remains without complete melting up to the surface layer.
  • the corrosion resistance after working is the result from punching a two-sided laminated metal sheet into a disk shape of a diameter of 158 mm, drawing it by a draw ratio of 1.56 so that the low melting point film becomes the inner surface to obtain a shallow drawn cup, then redrawing it by a draw ratio of 1.23 to obtain a can of a cup diameter of 82 mm and a cup height of 52 mm (DRD can), filling the inside with 2% citric acid, then storing it at 37 degrees for six months and examining the inside surface of the can for the state of corrosion.
  • PET-PBT is a mixed resin of polyethylene terephthalate and polybutylene terephthalate.
  • Two-layer PET is two-layer structure film with a surface layer of 10 ⁇ m PET (MP 265° C.) and a bottom layer of 10 ⁇ m PET-IA (MP about 150° C.).
  • PET-IA is polyethylene terephthalate/isophthalate copolymer.
  • PET is polyethylene terephthalate.
  • PP is polypropylene
  • PE is polyethylene
  • the two-sided laminated metal sheets of the present invention where the difference ⁇ Hz of the haze values of the low melting point film before and after bending is made 20% or less are superior in formability and corrosion resistance after working and are completely free of or exhibit almost no whitening when worked into a can or other container.
  • the difference ⁇ Hz of the haze values before and after bending is over 20%, whitening is observed when worked into a container and the formability and corrosion resistance after working are also inferior, it is learned.
  • the laminated metal sheet according to the present invention it is possible to adjust the thickness of the low melting point side film so as to simultaneously laminate two types of films with different melting points on the two sides of a metal sheet without sticking to the lamination rolls.
  • the high melting point film can be given sufficient hardness or strength and the film thickness can be made thinner and the cost further reduced.

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  • Physics & Mathematics (AREA)
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JP2003207664A JP4537673B2 (ja) 2002-10-17 2003-08-18 ラミネート金属板の製造方法
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JP2003343969A JP4183126B2 (ja) 2003-10-02 2003-10-02 缶容器用両面ラミネート金属板
PCT/JP2003/014945 WO2005016631A1 (ja) 2003-08-18 2003-11-21 ラミネート金属板とその製造方法

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US20120240756A1 (en) * 2010-12-21 2012-09-27 E. I. Du Pont De Nemours And Company Trauma Reducing Pack

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EP3339020A1 (de) * 2016-12-22 2018-06-27 Numan Sener Komposit-folie als verpackungsmaterial für lebensmittel
US10303822B2 (en) * 2017-03-30 2019-05-28 Livermore Software Technology Corp. Systems and methods of designing geometry of tool set in a numerical simulation of sheet metal forming operations including springback compensation
WO2019112051A1 (ja) * 2017-12-07 2019-06-13 日本製鉄株式会社 ヒートシール蓋及び缶

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EP1658955A1 (de) 2006-05-24
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AU2003284642A1 (en) 2005-03-07
DE60331007D1 (de) 2010-03-04
EP1658955A4 (de) 2007-08-08
US8551281B2 (en) 2013-10-08
EP1658955B2 (de) 2014-10-22
US20090133830A1 (en) 2009-05-28

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