US20060210817A1 - Resin film laminated metal sheet for can and method for fabricating the same - Google Patents
Resin film laminated metal sheet for can and method for fabricating the same Download PDFInfo
- Publication number
- US20060210817A1 US20060210817A1 US11/439,469 US43946906A US2006210817A1 US 20060210817 A1 US20060210817 A1 US 20060210817A1 US 43946906 A US43946906 A US 43946906A US 2006210817 A1 US2006210817 A1 US 2006210817A1
- Authority
- US
- United States
- Prior art keywords
- resin film
- film
- metal sheet
- resin
- laminated metal
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- 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
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- 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
- B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 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
- 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
- B32B2274/00—Thermoplastic elastomer material
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2307/746—Slipping, anti-blocking, low friction
-
- 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
- B32B2309/02—Temperature
-
- 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
- B32B2309/04—Time
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/30—Iron, e.g. steel
-
- 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
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- 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
-
- 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
-
- 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
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the present invention relates to a resin film laminated metal sheet to be mainly used to drums and caps of food stuffed cans, in particular resin film laminated metal sheet for can, which has excellent formability and adhesion while can-making and superior taking-out property of stuffed food contents, and to a method for fabricating the same.
- the object of these methods is to improve formability and adhesion of resin film laminated metal sheets, mainly ⁇ circle around (1) ⁇ by applying a resin film having a polar group such as a polyester resin (for example Japanese Patent Laid Open No. 63-236640) or ⁇ circle around (2) ⁇ by carrying out a treatment such as corona discharge on a surface of resin film so as to increase a surface free energy ⁇ s of resin film (for example, Japanese Patent Laid Open No. 5-200961).
- Japanese Patent Laid Open No. 5-200961 discloses that the ⁇ s of resin film should be specified in a range of 38 to 54 dyn/cm for securing adhesion after forming polyethylene film laminated metal sheets.
- This object can be accomplished by such a resin film laminated metal sheet for can, in which both faces of the metal sheet have resin film laminated layers, and a surface free energy ⁇ s of a face of the resin film is 10 dyn/cm or more to less than 30 dyn/cm, the face becoming an inside of can after can-making and being contacted with stuffed food contents.
- the resin film available is, for example, a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component.
- the resin film laminated metal sheet for can having such a resin film may be fabricated by a method comprising a step of laminating a resin film composed of a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component on the surface of the metal sheet which will become an inside of can after can-making, wherein the temperature of the metal sheet is above the melting point of the resin film after passing laminating rolls; otherwise by another method comprising a step of laminating a resin film of polyester being a main component on the surface of the metal sheet, wherein the temperature of the face of the resin film to be adhered to the metal sheet is above the melting point of the resin film between 1 and 20 msec.
- FIGS. 1A and 1B are cross sectional views of the resin film laminated metal sheet of the invention.
- FIG. 2 is a view showing one example of resin film laminating apparatus for metal sheet.
- FIG. 3 is a view showing another example of resin film laminating apparatus for metal sheet.
- the taking-out property has a close relation with a surface free energy ⁇ s of the resin film, and if the ⁇ s is more than 30 dyn/cm, the sticking between the resin film and the stuffed contents is excessive so that the taking-out property of stuffed food contents is poor. Accordingly, if the resin film of ⁇ s being less than 30 dyn/cm, more preferably less than 22 dyn/cm is, as seen in FIG.
- the ⁇ s of the face S 1 contacting stuffed food contents can be less than 30 dyn/cm, whereby it is possible to provide a resin film laminated metal sheet for can excellent in taking-out property of stuffed food contents.
- an ordinary resin film to be used to a resin film laminated metal sheet receives a surface activation treatment such as corona discharge, its ⁇ s is more than 30 dyn/cm.
- ⁇ s is more than 30 dyn/cm.
- the taking-out property is almost saturated, and since the fabrication of the resin film having such a ⁇ s is difficult, it should be 10 dyn/cm or more.
- the ⁇ s of the face of the resin film contacting an atmospheric air should be preferably determined to be 25 dyn/cm or higher.
- the ⁇ s of the faces S 2 and S 4 of the resin film shown in FIGS. 1A and 1B to be adhered to the metal sheet is smaller than the ⁇ s of the metal sheet so as to further improve the adhesion.
- the resin film of ⁇ s being 10 to less than 30 dyn/cm, available is a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component. Since these resin films have a molecular structure containing no polar group, the ⁇ s is low, and having good elongation and strength, they are advantageous for formability while can-making.
- a resin film having an adherent layer comprising a polar group composed of a polypropylene film modified with maleic acid anhydride or a propylene ethylene based random copolymer film modified with maleic acid anhydride
- the adhesion is improved while can-making and such a resin film can be applied to beverage cans requiring more excellent adhesion.
- the degree of crystallization of the resin film is more than 70%, the formability of the resin film is deteriorated and often causes breakage of film, and therefore preferably the degree of crystallization should be less than 70%, more preferably less than 60%.
- the resin film of polyester being a main component may be used as the resin film where the ⁇ s of the face to be an outside of can after can-making is 25 dyn/cm or higher.
- the resin film of polyester being a main component is defined by such a resin film containing polyester 50 mass % or more and further containing polyolefin and the like.
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- These resin films may be produced by melting a polymer resin under heating and shearing force through an extrusion machine, forming a wide and thin film through a T type die, instantly cooling by a chilled roll and coiling it, otherwise by an ordinary method of subjecting the resin film to biaxial orienting of longitudinal and lateral directions after passing through a T type die. Then, with respect to the resin film to be an inside of can after can-making, the treatment such as corona discharge for activating one surface is omitted.
- the resin film of polyester being a main component to the face contacting stuffed food contents, and containing a wax component of 0.1 to 2.0% in the resin film to be an inside of can after can-making, it is possible not only to lower ⁇ s of the resin film, but also to improve lubricity of the film surface, so that the taking-out property of stuffed food contents is improved by leaps and bounds, provided that if the wax component is contained less than 0.1%, an effect thereby is small, and if exceeding 2.0%, the effect is saturated and the film fabrication is difficult.
- the effect of the wax component cannot be provided by coating the wax component on the surface of the resin film. This is because the wax component pre-coated on the surface of the resin film is absorbed into the stuffed contents while retort-treatment which is conducted for sterilizing the contents after stuffing. If the wax component is contained in the resin film, as is the case of the present invention, the wax component is gradually thickened on the surface during the retort treatment, and therefore it is not all absorbed into the stuffed contents but the effect thereof can be usefully brought out.
- the wax component both of an organic and an inorganic lubricants are available, and the organic lubricant such as fatty acid ester is desirable, and among them, more preferable is a carnauba wax [a main component is CH 3 (CH 2 ) 24 COO(CH 2 ) 29 CH 3 and the other various components composed of aliphtic material and alcohol are contained] which is one of vegetable waxes and a natural wax, or stearic acid ester.
- a carnauba wax a main component is CH 3 (CH 2 ) 24 COO(CH 2 ) 29 CH 3 and the other various components composed of aliphtic material and alcohol are contained
- These wax components are easily added to the resin film of polyester being a main component due to their molecular structure.
- the polyester film containing the wax component is produced by mixing the wax component of a predetermined amount with polyester and passing through an ordinary film forming method.
- the resin film of polyester being a main component is a biaxial oriented polyester film where a relaxation time T1 ⁇ of benzene ring carbon of 1,4 coordination measured by a solid high resolution NMR is 150 msec or more. Because the biaxial oriented film is more excellent than a non-oriented film in characteristics such as tensile strength, tearing strength, impact strength, steam permeability, gas permeability and others.
- the relaxation time T1 ⁇ shows molecular maneuverability, and if the relaxation time T1 ⁇ is increased, the restraint force of non crystal parts in the resin film is increased.
- the relaxation time T1 ⁇ is set to be 150 msec or more, the above mentioned excellent effects can be exhibited, and even if a severe forming is performed after lamination, the excellent formability and the impact resistance can be provided.
- a high temperature preheating method and a high temperature orienting method are combined in the longitudinal orienting procedure when the resin film is produced. Otherwise, this is enabled by rationalizing, for example, an intrinsic viscosity of resin, a catalyst, an amount of diethylene glycol, orienting conditions, heat treating conditions and the like.
- the preheating temperature of the longitudinal orienting when producing the resin film is preferably 90° C. or higher, more preferably 100° C. or higher, and still more preferably 110° C. or higher.
- the orientating temperature is preferably 105° C. or higher, more preferably 110° C. or higher, and still more preferably 115° C. or higher.
- Polyester as the main component of the resin film is polymer composed of dicarboxylic acid and glycol.
- dicarboxylic acid applicable is terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or diphenyldicarboxylic acid, and among them, terephthalic acid or isophthalic acid is preferable.
- glycol there are enumerated ethylene glycol, propanediol and butanediol, and among them, ethylene glycol is preferable. More than two kinds of dicarboxylic acid or glycol may be used together.
- polyester may be, if required, mixed with anti-oxidant, heat stabilizer, ultraviolet asborbent, plasticizer, pigment, antistatic agent, or crystal nucleus.
- Polyester has excellent mechanical characteristics such as tensile strength, elastic modulus and impact strength, and has polarity, and therefore the formability and the adhesion of the resin film of polyester being a main component are improved up to the level durable to can-making and improve the impact resistance after can-making.
- the metal sheet applicable are aluminum sheets or soft steel sheets.
- optimum is a surface treated steel sheet (TFS) formed with double layered films comprising a lower layer of metallic chrome and an upper layer of chrome hydroxide.
- TFS surface treated steel sheet
- the metallic chrome layer is, in terms of chrome, 70 to 200 mg/m 2 and the chrome hydroxide is 10 to 30 mg/m 2 .
- the temperature of the metal sheet after passing laminating rolls should be above the melting point of the resin film.
- the resin film is substantially completely melted to increase fluidity, so that a wettability is improved to increase a contacting area with the metal surface, and the adhesion is improved. Since the crystal structure in the film is destroyed in company with melting of the film, crystal component obstructing the formability can be changed into non-crystal component, securing the formability of the resin film necessary for can-making.
- a time until cooling after passing the laminating rolls is 1 to 5 seconds. Being less than 1 second, since a wetting time is short, an enough contacting area cannot be secured, while exceeding 5 seconds, recrystallization of the film advances after passing the laminating rolls.
- the temperature of the metal sheet is set to be (the melting point of the resin film ⁇ 30)° C., the wetting on the metal surface is made more secure, and the recrystallization is validly controlled, enabling the degree of crystallization to be less than 70%.
- This effect is made more effective by setting to be (the melting point of the resin film ⁇ 10)° C., enabling the degree of crystallization to be less than 60%.
- An upper limit of the temperature is not especially defined, but it is desirable to be set at least less than (the melting point of the resin film+90)° C.
- the lamination should be carried out under the same conditions as mentioned above.
- a cooling is also effective during adhering.
- a surface pressure is preferably 1 to 30 kg/cm 2 . If the surface pressure is too low, the sufficient adhesion is difficult to realize because a time is short though being above the melting point, while if the surface pressure is large, a force loading to the laminating rolls is large, necessitating strength in facility and inviting a large scale in facility.
- a method of laminating the resin film on the metal surface is not limited to the above mentioned thermal adhesion method.
- the chrome plating was performed in a bath of CrO 3 , F ⁇ and SO 4 2 ⁇ , subjected to an intermediate rinse and thereafter to an electrolysis in a chemical conversion treatment solution containing CrO 3 and F ⁇ .
- electrolyzing conditions such as current density, amount of electricity
- the ⁇ s of the chrome plated steel sheet was evaluated by measuring a contact angle after a surface free energy-known liquid (pure water, glycerol, formamide, ethyleneglycol, dimethylglycol) was dropped on the steel surface at a humidity of 55 to 65% and at a temperature of 20° C.
- a surface free energy-known liquid pure water, glycerol, formamide, ethyleneglycol, dimethylglycol
- the resin film laminating apparatus for metal sheet shown in FIG. 2 was used in which the above mentioned chrome plated steel sheets 1 were heated in the heating apparatus 2 , and then laminated by the laminating rolls 3 with each kind of film 4 a shown in Table 1 on the face to be an inside of can after can-making and with PET film 4 b of ⁇ s being all 32 dyn/cm on the face to be an outside of can after can-making respectively through the thermal adhesion method.
- the resin film laminated metal sheets having 100 mm blank diameter were formed into cups at a drawing ratio (diameter before forming/diameter after forming) of 1.88 using a drawing machine.
- the contents of uniformly mixed eggs, meats oatmeals were stuffed in the cups, covered and followed by retort treatments (130° C. ⁇ 90 minutes). Thereafter, the cups were turned over, manually shaked two or three times, and after the contents were taken out, degrees of the contents remained within the cups were observed, and the taking-out properties of stuffed food contents were evaluated as follows.
- the resin film laminated metal sheet was coated with wax, punched into discs of 179 mm diameter, and formed into cups at a drawing ratio of 1.65.
- the cups were redrawn at a drawing ratio of 1.40.
- the observation of resin film of the above deep drawn cups was conducted, and the formability was evaluated as follows.
- the resin film laminating apparatus for metal sheet shown in FIG. 3 was used in which the same chrome plated steel sheets 1 as those of Example 1 were heated in the heating apparatus 2 , laminated by the laminating rolls 3 with various kinds of film 4 a shown in Table 2 on the face to be an inside of can after can-making and with PET film 4 b on the face to be an outside of can after can-making respectively, sprayed with the cooled water 8 controlled to be at constant temperature by the heat exchanger 13 from the spraying apparatus 14 in the cooling apparatus 5 so as to cool the films, and then pulled upward via the sink roll 7 from the cooling water tank 6 .
- the sheet temperature at the inlet of the laminating rolls 3 , the temperature of the laminating rolls 3 and the position of the spray apparatus 14 were controlled so as to variously change the sheet temperature immediately after passing the laminating rolls 3 , the time until starting of cooling after passing the laminating rolls 3 , and the sheet temperature at starting of cooling as shown in Table 2.
- the melting point of the resin film was calculated from the endothermic peaks obtained by means of a differential scanning calorimeter (DSC-2 made by Perkin-Elmar Inc.) under the conditions where samples were heated to 300° C. at a nitrogen flowing amount of 20 ml/min and at a heating rate of 10° C./min.
- DSC-2 differential scanning calorimeter
- the degree of crystallization of the resin film was measured as follows.
- the density of the resin film adopted by melting the metal part of the resin film laminated metal sheet was obtained by a density gradient method, and the degree of crystallization of the resin film was calculated by the following equation.
- X [ ⁇ ( 1/ dam ) ⁇ (1/ d ⁇ / ⁇ (1/ dam ) ⁇ (1/ dc ) ⁇ ] ⁇ 100
- the density gradient method was carried out by the density gradient pipe of JIS K 7112 as follows.
- the inventive examples show that the degrees of crystallization of the resin film are all less than 70%, and each of the properties is excellent.
- the degree of crystallization of the film is less than 60° C., and more excellent formability and adhesion may be obtained.
- the degrees of crystallization of the films of the comparative examples 1, 3, 4 are 70% or more, and the formability and the adhesion are inferior.
- the taking-out property is poor.
- the resin film laminating apparatus for metal sheet shown in FIG. 2 was used in which the chrome plated steel sheets of the chrome amount being 120 mg/m 2 and the chrome hydroxide amount being 15 mg/m 2 fabricated in the same method in Example 1 were heated in the metal sheet heating apparatus 2 , and the laminating rolls 3 laminated the film 4 a on the face of the steel sheets to be an inside of can after can-making and laminated the resin film 4 b on the face of them to be an outside of can after can-making. At that time, as the resin film 4 a on the inside of can after can-making, the resin film 4 b on the outside of can after can-making which was added with wax was used.
- Table 3 shows the laminated resin films and the laminating temperature conditions. The laminating rolls 3 were internal cooling rolls, and the cooling water was forcibly circulated during laminating so as to carry out the cooling while adhering the film.
- Example 1 With respect to the thus produced resin film laminated metal sheets, the formability and the adhesion after forming were evaluated in the same ways as Example 1. The taking-out properties of stuffed food contents were evaluated in the following 3 steps more in detail than Example 1.
- a spectrometer JNM-GX270 made by Japan Electron Optics Laboratory Co., Ltd.
- a solid amplifier made by the same
- MAS controller NM-GSH27MU a probe NM-GSH27T made by the same.
- T1 ⁇ vertical relaxation in the rotational coordinate
- the measuring conditions were temperature of 24.5° C., humidity of 50% RH, static magnetic field of 6.34 T (Tesla), and resonant frequencies of 1 H, 13 C being 270.2 MHz and 67.9 MHz respectively.
- MAS (rotation of magic angle) method was employed for canceling influences of anisotropy of chemical shift.
- the rotation number was 3.5 to 3.7 kHz.
- the conditions of pulse series were 90° for 1 H, pulse width of 4 ⁇ sec, the strength of rocking magnetic field of 62.5 kHz.
- the contacting time of CP (cross polarization) for shifting the polarization of 1 H to 13 C was 1.5 msec.
- As the holding times ⁇ 0.001, 0.5, 0.7, 1.3, 7, 10, 20, 30, 40, 50 msec were used.
- Free induction decrement (FID) of 13 C magnetization vector after the holding time ⁇ was measured (a high output coupling was done for removing influences of dipole mutual action by 1 H during measuring FID. For improving S/N, integrations were made 512 times.).
- the pulse repeating time was between 5 and 15 sec.
- T1 ⁇ values can be ordinarily described by the following equation and can be obtained from the slope when the peak strength measured for each of the holding times is plotted in a scale of semi-logarithm.
- I ( t ) ⁇ ( Ai )exp( ⁇ t/T 1 ⁇ i )
- the melting point was measured at a heating rate of 10° C./min by the same differential scanning calorimeter as described above.
- the inventive examples are all excellent in the taking-out property of stuffed food contents, the formability, the adhesion, and the impact resistance.
- the relaxation time T1 ⁇ is 150 msec or more, or the time when the temperature of the resin film contacting the metal sheet goes above the melting point of the resin film, is 1 to 20 msec
- the formability, the adhesion and the impact resistance are more excellent.
- the comparative examples 1 to 3 are poor in the taking-out property of food stuffed contents, and the comparative examples 4 and 5 are inferior in the formability.
Landscapes
- Laminated Bodies (AREA)
Abstract
The present invention relates to a resin film laminated metal sheet for can, in which both faces of the metal sheet have resin film laminated layers, and a surface free energy γ s of a face of the resin film is 10 dyn/cm or more to less than 30 dyn/cm, the face becoming an inside of can after can-making and being contacted with stuffed food contents. As the resin film, applicable is a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component. Further, a resin film of polyester being a main component and containing a wax component of 0.1 to 2.0% is used in a resin film to be an inside of can after can-making. The resin film laminated metal sheet for can according to the invention has excellent formability and adhesion while can-making and superior taking-out property of stuffed food contents.
Description
- This is a Divisional application of Ser. No. 10/719,797 filed Nov. 20, 2003 (now pending) which is a Divisional application of Ser. No. 09/665,323 filed Sep. 19, 2000 (now U.S. Pat. No. 6,723,441).
- 1. Field of the Invention
- The present invention relates to a resin film laminated metal sheet to be mainly used to drums and caps of food stuffed cans, in particular resin film laminated metal sheet for can, which has excellent formability and adhesion while can-making and superior taking-out property of stuffed food contents, and to a method for fabricating the same.
- 2. Description of Related Art
- Conventionally, coatings have been carried out on metal sheets such as tin free steel (TFS) or aluminum as blank materials for can to be used to food stuffed cans. The coating technique was involved with many problems of being complicated in a baking procedure, taking much treating time, or exhausting much solvent. Therefore, instead of coating, a lot of methods have been proposed for laminating a thermoplastic resin film to heated metal sheets.
- The object of these methods is to improve formability and adhesion of resin film laminated metal sheets, mainly {circle around (1)} by applying a resin film having a polar group such as a polyester resin (for example Japanese Patent Laid Open No. 63-236640) or {circle around (2)} by carrying out a treatment such as corona discharge on a surface of resin film so as to increase a surface free energy γ s of resin film (for example, Japanese Patent Laid Open No. 5-200961). In particular, Japanese Patent Laid Open No. 5-200961 discloses that the γ s of resin film should be specified in a range of 38 to 54 dyn/cm for securing adhesion after forming polyethylene film laminated metal sheets.
- On the other hand, there is a problem that if such a resin film laminated metal sheet is applied to food stuffed cans, when removing fully stuffed food contents from the can, it is difficult to take out them because they are firmly stuck to an inside of the can. This problem weakens consumers' purchasing desires, and a resolution of the problem is seriously important, however up to now no investigation has been ever performed.
- It is accordingly an object of the invention to provide a resin film laminated metal sheet for can, which is excellent in formability and adhesion while can-making and in taking-out property of stuffed food contents, and a method for fabricating the same.
- This object can be accomplished by such a resin film laminated metal sheet for can, in which both faces of the metal sheet have resin film laminated layers, and a surface free energy γ s of a face of the resin film is 10 dyn/cm or more to less than 30 dyn/cm, the face becoming an inside of can after can-making and being contacted with stuffed food contents.
- As the resin film, available is, for example, a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component.
- It is more effective to use a resin film of polyester being a main component and contain a wax component of 0.1 to 2.0% in the resin film which will be an inside of can after can-making.
- The resin film laminated metal sheet for can having such a resin film may be fabricated by a method comprising a step of laminating a resin film composed of a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component on the surface of the metal sheet which will become an inside of can after can-making, wherein the temperature of the metal sheet is above the melting point of the resin film after passing laminating rolls; otherwise by another method comprising a step of laminating a resin film of polyester being a main component on the surface of the metal sheet, wherein the temperature of the face of the resin film to be adhered to the metal sheet is above the melting point of the resin film between 1 and 20 msec.
-
FIGS. 1A and 1B are cross sectional views of the resin film laminated metal sheet of the invention; -
FIG. 2 is a view showing one example of resin film laminating apparatus for metal sheet; and -
FIG. 3 is a view showing another example of resin film laminating apparatus for metal sheet. - We earnestly studied the relation between the resin film and the taking-out property of stuffed food contents in a resin film laminated metal sheet for can, and consequently found that the taking-out property has a close relation with a surface free energy γ s of the resin film, and if the γ s is more than 30 dyn/cm, the sticking between the resin film and the stuffed contents is excessive so that the taking-out property of stuffed food contents is poor. Accordingly, if the resin film of γ s being less than 30 dyn/cm, more preferably less than 22 dyn/cm is, as seen in
FIG. 1A , laminated on a face of the metal sheet which will be an inside of can after can-making, the γ s of the face S1 contacting stuffed food contents can be less than 30 dyn/cm, whereby it is possible to provide a resin film laminated metal sheet for can excellent in taking-out property of stuffed food contents. - As mentioned above, since an ordinary resin film to be used to a resin film laminated metal sheet receives a surface activation treatment such as corona discharge, its γ s is more than 30 dyn/cm. For setting γ s to be less than 30 dyn/cm, it is necessary to select an appropriate resin film, and to omit the surface activation treatment such as corona discharge. This omission does not cause any problem in the fabrication of the resin film, but is advantageous in production cost.
- As far as the γ s is less than 10 dyn/cm, the taking-out property is almost saturated, and since the fabrication of the resin film having such a γ s is difficult, it should be 10 dyn/cm or more.
- Even if using the resin film of γ s of not less than 10 dyn/cm to less than 30 dyn/cm, the formability and the adhesion are not spoiled while can-making.
- Ordinarily, to the outside face S3 of can shown in
FIG. 1B , since trade names or trade marks are printed, a wettability to ink should be improved, and therefore, the γ s of the face of the resin film contacting an atmospheric air should be preferably determined to be 25 dyn/cm or higher. - It is preferable that the γ s of the faces S2 and S4 of the resin film shown in
FIGS. 1A and 1B to be adhered to the metal sheet is smaller than the γ s of the metal sheet so as to further improve the adhesion. - As the resin film of γ s being 10 to less than 30 dyn/cm, available is a polypropylene film or a propylene ethylene based random copolymer film of polypropylene being a main component. Since these resin films have a molecular structure containing no polar group, the γ s is low, and having good elongation and strength, they are advantageous for formability while can-making.
- Further, if using, to the face S2 contacting the metal sheet shown in
FIG. 1A , for example, a resin film having an adherent layer comprising a polar group composed of a polypropylene film modified with maleic acid anhydride or a propylene ethylene based random copolymer film modified with maleic acid anhydride, the adhesion is improved while can-making and such a resin film can be applied to beverage cans requiring more excellent adhesion. - When the polypropylene film or the propylene ethylene based random copolymer film as mentioned above is laminated on the metal sheet, a thermal adhesion method is ordinarily employed. At this time, if a degree of crystallization of the resin film is more than 70%, the formability of the resin film is deteriorated and often causes breakage of film, and therefore preferably the degree of crystallization should be less than 70%, more preferably less than 60%.
- As the resin film where the γ s of the face to be an outside of can after can-making is 25 dyn/cm or higher, the resin film of polyester being a main component may be used. The resin film of polyester being a main component is defined by such a resin film containing polyester 50 mass % or more and further containing polyolefin and the like. For example, PET (polyethylene terephthalate) film having excellent formability is suited.
- These resin films may be produced by melting a polymer resin under heating and shearing force through an extrusion machine, forming a wide and thin film through a T type die, instantly cooling by a chilled roll and coiling it, otherwise by an ordinary method of subjecting the resin film to biaxial orienting of longitudinal and lateral directions after passing through a T type die. Then, with respect to the resin film to be an inside of can after can-making, the treatment such as corona discharge for activating one surface is omitted.
- If using the resin film of polyester being a main component to the face contacting stuffed food contents, and containing a wax component of 0.1 to 2.0% in the resin film to be an inside of can after can-making, it is possible not only to lower γ s of the resin film, but also to improve lubricity of the film surface, so that the taking-out property of stuffed food contents is improved by leaps and bounds, provided that if the wax component is contained less than 0.1%, an effect thereby is small, and if exceeding 2.0%, the effect is saturated and the film fabrication is difficult.
- The effect of the wax component cannot be provided by coating the wax component on the surface of the resin film. This is because the wax component pre-coated on the surface of the resin film is absorbed into the stuffed contents while retort-treatment which is conducted for sterilizing the contents after stuffing. If the wax component is contained in the resin film, as is the case of the present invention, the wax component is gradually thickened on the surface during the retort treatment, and therefore it is not all absorbed into the stuffed contents but the effect thereof can be usefully brought out.
- As the wax component, both of an organic and an inorganic lubricants are available, and the organic lubricant such as fatty acid ester is desirable, and among them, more preferable is a carnauba wax [a main component is CH3(CH2)24COO(CH2)29CH3 and the other various components composed of aliphtic material and alcohol are contained] which is one of vegetable waxes and a natural wax, or stearic acid ester. These wax components are easily added to the resin film of polyester being a main component due to their molecular structure. The polyester film containing the wax component is produced by mixing the wax component of a predetermined amount with polyester and passing through an ordinary film forming method.
- When aiming at an application of the present resin film to a can such as DTR can which receives a severe forming, it is preferable that the resin film of polyester being a main component is a biaxial oriented polyester film where a relaxation time T1ρ of benzene ring carbon of 1,4 coordination measured by a solid high resolution NMR is 150 msec or more. Because the biaxial oriented film is more excellent than a non-oriented film in characteristics such as tensile strength, tearing strength, impact strength, steam permeability, gas permeability and others. Herein, the relaxation time T1ρ shows molecular maneuverability, and if the relaxation time T1ρ is increased, the restraint force of non crystal parts in the resin film is increased. Thereby, crystallization of non crystal parts can be controlled while can-making. That is, the maneuverability of the non crystal parts is reduced and the re-orientating for crystallization is controlled. If the relaxation time T1ρ is set to be 150 msec or more, the above mentioned excellent effects can be exhibited, and even if a severe forming is performed after lamination, the excellent formability and the impact resistance can be provided.
- As a way for exceeding the relaxation time T1ρ above 150 msec, a high temperature preheating method and a high temperature orienting method are combined in the longitudinal orienting procedure when the resin film is produced. Otherwise, this is enabled by rationalizing, for example, an intrinsic viscosity of resin, a catalyst, an amount of diethylene glycol, orienting conditions, heat treating conditions and the like. The preheating temperature of the longitudinal orienting when producing the resin film is preferably 90° C. or higher, more preferably 100° C. or higher, and still more preferably 110° C. or higher. The orientating temperature is preferably 105° C. or higher, more preferably 110° C. or higher, and still more preferably 115° C. or higher.
- Polyester as the main component of the resin film is polymer composed of dicarboxylic acid and glycol. As the dicarboxylic acid, applicable is terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or diphenyldicarboxylic acid, and among them, terephthalic acid or isophthalic acid is preferable. As a glycol, there are enumerated ethylene glycol, propanediol and butanediol, and among them, ethylene glycol is preferable. More than two kinds of dicarboxylic acid or glycol may be used together. Further, polyester may be, if required, mixed with anti-oxidant, heat stabilizer, ultraviolet asborbent, plasticizer, pigment, antistatic agent, or crystal nucleus.
- Polyester has excellent mechanical characteristics such as tensile strength, elastic modulus and impact strength, and has polarity, and therefore the formability and the adhesion of the resin film of polyester being a main component are improved up to the level durable to can-making and improve the impact resistance after can-making.
- In the above mentioned resin film laminated metal sheet for can according to the invention, no limitation is especially defined to thickness of the resin film which will be an inside or outside of can after can-making. Ordinary thickness of around 10 to 50 μm is sufficient.
- Further, as the metal sheet, applicable are aluminum sheets or soft steel sheets. In particular, optimum is a surface treated steel sheet (TFS) formed with double layered films comprising a lower layer of metallic chrome and an upper layer of chrome hydroxide. Also in this case, no limitation is especially made to amounts of the metallic chrome layer and the chrome hydroxide layer of TFS, but in view of the adhesion and the corrosion resistance after can-making, it is desirable that the metallic chrome layer is, in terms of chrome, 70 to 200 mg/m2 and the chrome hydroxide is 10 to 30 mg/m2.
- With respect to the fabrication method thereof, when laminating the resin film composed of polypropylene film or propylene ethylene based random copolymer film of polypropylene being a main component on the surface of the metal sheet which will be an inside of can after can-making, the temperature of the metal sheet after passing laminating rolls (adhesion pressing rolls) should be above the melting point of the resin film. Thereby, when laminating, the resin film is substantially completely melted to increase fluidity, so that a wettability is improved to increase a contacting area with the metal surface, and the adhesion is improved. Since the crystal structure in the film is destroyed in company with melting of the film, crystal component obstructing the formability can be changed into non-crystal component, securing the formability of the resin film necessary for can-making.
- Then, it is desirable that a time until cooling after passing the laminating rolls is 1 to 5 seconds. Being less than 1 second, since a wetting time is short, an enough contacting area cannot be secured, while exceeding 5 seconds, recrystallization of the film advances after passing the laminating rolls. In addition to these conditions, if the temperature of the metal sheet is set to be (the melting point of the resin film−30)° C., the wetting on the metal surface is made more secure, and the recrystallization is validly controlled, enabling the degree of crystallization to be less than 70%. This effect is made more effective by setting to be (the melting point of the resin film−10)° C., enabling the degree of crystallization to be less than 60%. An upper limit of the temperature is not especially defined, but it is desirable to be set at least less than (the melting point of the resin film+90)° C.
- Also in case the resin film has a resin layer having a polar group in the face adhering the metal sheet, the lamination should be carried out under the same conditions as mentioned above.
- On the other hand, when laminating the resin film of polyester being a main component on the metal surface, it is necessary that the temperature of the face of the resin film adhering the metal sheet is above the melting point of the resin film between 1 and 20 msec. Being less than 1 msec, it is not sufficient for the resin film to adhere the metal sheet, while exceeding 20 msec, the controlling performance of the molecular maneuverability in the vicinity of the face adhering the metal sheet is lost.
- For getting the above effects, in addition to the lamination at a high speed, a cooling is also effective during adhering. No limitation is especially defined to pressing when laminating, but a surface pressure is preferably 1 to 30 kg/cm2. If the surface pressure is too low, the sufficient adhesion is difficult to realize because a time is short though being above the melting point, while if the surface pressure is large, a force loading to the laminating rolls is large, necessitating strength in facility and inviting a large scale in facility.
- A method of laminating the resin film on the metal surface is not limited to the above mentioned thermal adhesion method.
- A steel sheet of 0.18 mm thickness and 977 mm width having passed through cold rolling, annealing and temper rolling was degreased and pickled, followed by chrome plating. The chrome plating was performed in a bath of CrO3, F− and SO4 2−, subjected to an intermediate rinse and thereafter to an electrolysis in a chemical conversion treatment solution containing CrO3 and F−. At that time, electrolyzing conditions (such as current density, amount of electricity) were changed to control amount of metallic chrome, amount of chrome hydroxide and γ s.
- The γ s of the chrome plated steel sheet was evaluated by measuring a contact angle after a surface free energy-known liquid (pure water, glycerol, formamide, ethyleneglycol, dimethylglycol) was dropped on the steel surface at a humidity of 55 to 65% and at a temperature of 20° C.
- The resin film laminating apparatus for metal sheet shown in
FIG. 2 was used in which the above mentioned chrome platedsteel sheets 1 were heated in theheating apparatus 2, and then laminated by the laminating rolls 3 with each kind offilm 4 a shown in Table 1 on the face to be an inside of can after can-making and withPET film 4 b of γ s being all 32 dyn/cm on the face to be an outside of can after can-making respectively through the thermal adhesion method. - Thus produced resin film laminated metal sheets were subjected to the measurement of γ s by the above mentioned method, and to the evaluation of taking-out property of stuffed food contents 1), formability 2) and adhesion after forming 3) by the following methods.
- 1) Taking-Out Property of Stuffed Food Contents
- The resin film laminated metal sheets having 100 mm blank diameter were formed into cups at a drawing ratio (diameter before forming/diameter after forming) of 1.88 using a drawing machine. The contents of uniformly mixed eggs, meats oatmeals were stuffed in the cups, covered and followed by retort treatments (130° C.×90 minutes). Thereafter, the cups were turned over, manually shaked two or three times, and after the contents were taken out, degrees of the contents remained within the cups were observed, and the taking-out properties of stuffed food contents were evaluated as follows.
-
- ◯: The taking-out is easy, and no stuck food remains in the inside of the cup.
- ×: The taking-out is hard by shaking by hands, and the stuck food can not be taken out without using a spoon or the like.
2) Formability
- The resin film laminated metal sheet was coated with wax, punched into discs of 179 mm diameter, and formed into cups at a drawing ratio of 1.65. The cups were redrawn at a drawing ratio of 1.40. The observation of resin film of the above deep drawn cups was conducted, and the formability was evaluated as follows.
-
- {circle around (∘)}: No injury exists in the film after forming, and no whiting is recognized therein.
- ◯: The forming is possible, but the whiting is recognized.
- ×: The cup is broken at the barrel, and the forming is impossible.
3) Adhesion After Forming
- From the barrel of the cup formed in the above 2), samples (15 mm width and 120 mm length) were cut out for peeling tests. The resin film was partially delaminated from the edge of the face of the cut-out sample, corresponding to the inside of the cup, and the delaminated film was peeled out by a tensile tester in an opposite direction (angle 180°) to the chrome plated steel sheet at a tensile rate of 30 mm/min. Then the adhesion force was measured and the adhesion after forming was evaluated as follows.
-
- {circle around (∘)}: 0.15 kg/15 mm or more
- ◯: 0.10 kg/15 mm or more to less than 0.15 kg/15 mm
- ×: Less than 0.10 kg/15 mm
- As shown in Table 1. The inventive examples are all excellent, while the comparative examples are inferior in the taking-out property of stuffed food contents.
TABLE 1 Film laminated steel sheet Chrome plated steel sheet Face corresponding to an Cr coating inside after can-making Evaluation of performance weight Surface Surface Taking-out Metallic Cr free Film free property chrome oxide energy thickness energy 3) of stuffed No. (mg/m2) (mg/m2) (dyn/cm) Film types 1) (μ) (dyn/cm) contents Formability Adhesion E1 120 15 35 PP 30 18 ◯ ⊚ ⊚ E2 ″ ″ 35 PP - PE Mixture ″ 19 ◯ ⊚ ⊚ E3 ″ ″ 35 PP + Adhered 20 18 ◯ ⊚ ⊚ layer 2) E4 ″ ″ 30 PP 15 18 ◯ ⊚ ⊚ E5 ″ ″ 35 PE 30 19 ◯ ⊚ ⊚ E6 ″ ″ 30 PTFE ″ 12 ◯ ◯ ◯ E7 120 10 20 PP ″ 18 ◯ ◯ ◯ C1 120 15 35 PP + Corona ″ 35 X ⊚ ⊚ discharge treatment (both sides) C2 ″ ″ 35 PET ″ 32 X ⊚ ⊚
Note 1)
PP: Polypropylene film
PE: Polyethylene film
PP - PE Mixture: Propylene ethylene based random copolymer film
PTFE: Polytetorafluoroethylene film (poly-4-ethylene fluoride film)
PET: Polyethylene terephthalate film
Note 2)
Adhered layer: Maleic acid anhydride graft modified polypropylene resin. Film thickness 5μ
Note 3)
Surface free energy is equivalent in both surfaces excepting the Inventive example 3, Side of adhered layer of the Inventive example 3 is 32 dyn/cm
E: Example
C: Comparative example
- The resin film laminating apparatus for metal sheet shown in
FIG. 3 was used in which the same chrome platedsteel sheets 1 as those of Example 1 were heated in theheating apparatus 2, laminated by the laminating rolls 3 with various kinds offilm 4 a shown in Table 2 on the face to be an inside of can after can-making and withPET film 4 b on the face to be an outside of can after can-making respectively, sprayed with the cooledwater 8 controlled to be at constant temperature by the heat exchanger 13 from the sprayingapparatus 14 in thecooling apparatus 5 so as to cool the films, and then pulled upward via thesink roll 7 from the coolingwater tank 6. At that time, the sheet temperature at the inlet of the laminating rolls 3, the temperature of the laminating rolls 3 and the position of thespray apparatus 14 were controlled so as to variously change the sheet temperature immediately after passing the laminating rolls 3, the time until starting of cooling after passing the laminating rolls 3, and the sheet temperature at starting of cooling as shown in Table 2. - With respect to the thus produced resin film laminated metal sheets, the taking-out property of stuffed food contents, the formability and the adhesion after forming were evaluated in the same ways as Example 1.
- The melting point of the resin film was calculated from the endothermic peaks obtained by means of a differential scanning calorimeter (DSC-2 made by Perkin-Elmar Inc.) under the conditions where samples were heated to 300° C. at a nitrogen flowing amount of 20 ml/min and at a heating rate of 10° C./min.
- The degree of crystallization of the resin film was measured as follows.
- 4) Degree of Crystallization of the Resin Film After Lamination
- The density of the resin film adopted by melting the metal part of the resin film laminated metal sheet was obtained by a density gradient method, and the degree of crystallization of the resin film was calculated by the following equation.
X=[{(1/dam)−(1/d}/{(1/dam)−(1/dc)}]×100 - Herein,
-
- X: Degree (%) of crystallization of the film
- dam: Density (0.860 g/cc) of completely amorphous polypropylene resin
- dc: Density (0.938 g/cc) of completely crystallized polypropylene resin
- d: Density (g/cc) of the resin film after lamination
- The density gradient method was carried out by the density gradient pipe of JIS K 7112 as follows.
- i) The density gradient pipe is made using a high density and a low density solutions.
- ii) The relation between the depth of water of the density gradient pipe and the density is measured using a float having a known specific gravity.
- iii) A sample is laid in the density gradient pipe, and after 2 hr a position where the sample stands still (the depth of water) is read out.
- iv) The density of the sample is calculated from the relation between the depth of water of the density gradient pipe and the density.
- As shown in Table 2, the inventive examples show that the degrees of crystallization of the resin film are all less than 70%, and each of the properties is excellent. In particular, when the temperature of the metal sheet was above (the melting point of the resin film−10)° C. at starting of cooling, the degree of crystallization of the film is less than 60° C., and more excellent formability and adhesion may be obtained.
- On the other hand, the degrees of crystallization of the films of the comparative examples 1, 3, 4 are 70% or more, and the formability and the adhesion are inferior. In the comparative example 2 where PET was used to the face to be an inside of can after can-making, the taking-out property is poor.
TABLE 2 Laminating conditions Degree Laminated film Sheet T. Time until of Chrome plated Face corresponding immediately start of crystal- steel sheet to an inside after after cooling Sheet lization Evaluation of Cr coating can-making passing after the T. at of film performance weight Film Melting the passing starting after Taking-out Metallic Cr thick- point of laminating laminating of lamina- property chrome oxide Film types ness film rolls rolls cooling tion of stuffed Form- Adhe- No. (mg/m2) (mg/m2) 1), 2) (μm) (° C.) (° C.) (sec) (° C.) (%) contents ability sion E1 120 15 PP + 20 165 180 2 170 52 ◯ ⊚ ⊚ Adhered layer E2 120 15 PP + 20 165 175 1 170 54 ◯ ⊚ ⊚ Adhered layer E3 120 15 PP + 20 165 182 3 177 52 ◯ ⊚ ⊚ Adhered layer E4 120 15 PP + 20 165 165 4 145 65 ◯ ◯ ⊚ Adhered layer E5 120 15 PP + 20 165 182 5 162 58 ◯ ⊚ ⊚ Adhered layer E6 120 15 PP + 30 145 160 3 145 58 ◯ ⊚ ⊚ Adhered layer E7 120 15 PP + 30 145 145 3 130 63 ◯ ◯ ⊚ Adhered layer E8 120 15 PP - 30 165 180 3 165 52 ◯ ⊚ ⊚ PE Mixture E9 120 15 PP 20 165 180 3 165 52 ◯ ⊚ ⊚ E10 120 15 PP + 20 165 180 1 177 50 ◯ ⊚ ◯ Adhered layer E11 120 15 PP + 20 165 180 6 150 63 ◯ ◯ ◯ Adhered layer E12 120 15 PP + 20 165 165 7 130 68 ◯ ◯ ◯ Adhered layer C1 120 15 PE 30 120 120 2 110 40 ◯ X X C2 120 15 PET 20 220 180 2 170 20 X ⊚ ⊚ C3 120 15 PP + 20 165 155 2 145 78 ◯ X X Adhered layer C4 120 15 PP + 20 165 150 1 145 74 ◯ X X Adhered layer
Note 1)
PP: Polypropylene film
PP + PE Mixture: Propylene ethylene based random copolymer film
PE: Polyethylene film
PET: Polyethylene terephthalate film
Note 2)
Adhered layer: Maleic acid anhydride graft modified polypropylene resin.Film thickness 5 μm
E: Example
C: Comparative example
T.: Temperature
- The resin film laminating apparatus for metal sheet shown in
FIG. 2 was used in which the chrome plated steel sheets of the chrome amount being 120 mg/m2 and the chrome hydroxide amount being 15 mg/m2 fabricated in the same method in Example 1 were heated in the metalsheet heating apparatus 2, and the laminating rolls 3 laminated thefilm 4 a on the face of the steel sheets to be an inside of can after can-making and laminated theresin film 4 b on the face of them to be an outside of can after can-making. At that time, as theresin film 4 a on the inside of can after can-making, theresin film 4 b on the outside of can after can-making which was added with wax was used. Table 3 shows the laminated resin films and the laminating temperature conditions. The laminating rolls 3 were internal cooling rolls, and the cooling water was forcibly circulated during laminating so as to carry out the cooling while adhering the film. - With respect to the thus produced resin film laminated metal sheets, the formability and the adhesion after forming were evaluated in the same ways as Example 1. The taking-out properties of stuffed food contents were evaluated in the following 3 steps more in detail than Example 1.
-
- {circle around (∘)}: The taking-out is easy, and no stuck food remains in the inside of the cup.
- ◯: The taking-out is hard only by shaking by hands, but stuck food can be taken out by a spoon or the like, and little food stuck to the inside of the cup are left.
- ×: The taking-out is hard only by shaking by hands, and stuck food can be taken out by a spoon or the like. Much food is left in the inside of the cup after taking out.
- Further, the relaxation time T1ρ, the melting point of polyester and the impact resistance were measured as follows.
- 5) Relaxation Time T1ρ of Polyester
- For measuring solid NMR, used were a spectrometer JNM-GX270 made by Japan Electron Optics Laboratory Co., Ltd., a solid amplifier made by the same, MAS controller NM-GSH27MU, and a probe NM-GSH27T made by the same. The measurement of T1ρ (vertical relaxation in the rotational coordinate) of 13C nucleus was practiced. The measuring conditions were temperature of 24.5° C., humidity of 50% RH, static magnetic field of 6.34 T (Tesla), and resonant frequencies of 1H, 13C being 270.2 MHz and 67.9 MHz respectively. MAS (rotation of magic angle) method was employed for canceling influences of anisotropy of chemical shift. The rotation number was 3.5 to 3.7 kHz. The conditions of pulse series were 90° for 1H, pulse width of 4 μsec, the strength of rocking magnetic field of 62.5 kHz. The contacting time of CP (cross polarization) for shifting the polarization of 1H to 13C was 1.5 msec. As the holding times τ, 0.001, 0.5, 0.7, 1.3, 7, 10, 20, 30, 40, 50 msec were used. Free induction decrement (FID) of 13C magnetization vector after the holding time τ was measured (a high output coupling was done for removing influences of dipole mutual action by 1H during measuring FID. For improving S/N, integrations were made 512 times.). The pulse repeating time was between 5 and 15 sec.
- T1ρ values can be ordinarily described by the following equation and can be obtained from the slope when the peak strength measured for each of the holding times is plotted in a scale of semi-logarithm.
I(t)=Σ(Ai)exp(−t/T1ρi) -
- Ai: Percentage of components with respect to T1ρi
- Herein, analyses were made by the 2 components (T1ρ1: Non-crystal component, T1ρ2: Crystal component), and the following equation was used so as to obtain the value by a least square method.
I(t)=fa1·exp(−t/T1ρ1)+fa2·exp(−t/T1ρ2) -
- fa1: Percentage of components with respect to T1ρ1
- fa2: Percentage of components with respect to T1ρ2
fa1+fa2=1 - herein, T1ρ2 is used for T1ρ1.
6) Melting Point of Polyester
- After crystallizing polyester, the melting point was measured at a heating rate of 10° C./min by the same differential scanning calorimeter as described above.
- 7) Impact Resistance
- With respect to the cups formed in the above 2) for the evaluation of the formability, those were filled with water, 10 cups per each of tests were dropped on a vinyl chloride floor from a height of 1.25 m, then the voltage of 6 V was supplied to the electrodes and the cups for reading the current after 3 seconds, and the impact resistances were evaluated as follows.
-
- {circle around (∘)}: Less than 0.01 mA
- ◯: 0.01 mA or more to less than 0.1 mA
- ×: 0.1 mA or more
- As shown in Table 3, the inventive examples are all excellent in the taking-out property of stuffed food contents, the formability, the adhesion, and the impact resistance. In particular, in the inventive examples where the relaxation time T1ρis 150 msec or more, or the time when the temperature of the resin film contacting the metal sheet goes above the melting point of the resin film, is 1 to 20 msec, the formability, the adhesion and the impact resistance are more excellent. On the other hand, the comparative examples 1 to 3 are poor in the taking-out property of food stuffed contents, and the comparative examples 4 and 5 are inferior in the formability.
TABLE 3 Sheet T. at starting Time at Wax6) Film of above Taking-out Clas- Addition Melting thick- lamina- melting property Form- Impact sifi- amount point ness T1ρ tion point of stuffed abil- Adhe- resis- cation Film Types (wt %) (° C.) (μm) (msec) (° C.) (msec) contents ity sion tance E1 PET1) Carnauba 0.50 255 15 220 282 15 ⊚ ⊚ ⊚ ⊚ E2 PET Carnauba 0.75 255 15 220 282 15 ⊚ ⊚ ⊚ ⊚ E3 PET Carnauba 0.10 255 15 220 282 15 ◯ ⊚ ⊚ ⊚ E4 PET Carnauba 1.50 255 15 220 282 15 ⊚ ⊚ ⊚ ⊚ E5 PET Stearylstearey2) 0.50 255 15 220 282 15 ⊚ ⊚ ⊚ ⊚ E6 PET Stearylstearey 0.75 255 15 220 282 15 ⊚ ⊚ ⊚ ⊚ E7 PET Silicone 1.50 255 15 220 282 15 ◯ ⊚ ⊚ ⊚ E8 PET Carnauba 0.50 255 15 400 282 15 ⊚ ⊚ ⊚ ⊚ E9 PET Carnauba 0.50 255 15 160 282 15 ⊚ ⊚ ⊚ ⊚ E10 PET Carnauba 0.50 255 15 120 282 15 ⊚ ◯ ◯ ◯ E11 PET Carnauba 0.50 255 15 220 260 3 ⊚ ⊚ ⊚ ⊚ E12 PET Carnauba 0.50 255 15 220 255 0.5 ⊚ ◯ ◯ ◯ E13 PET Carnauba 0.50 255 15 220 293 25 ⊚ ◯ ◯ ◯ E14 PET/I3) Carnauba 0.50 226 15 210 282 20 ⊚ ⊚ ⊚ ⊚ E15 PET Carnauba 0.50 255 25 220 282 15 ⊚ ⊚ ⊚ ⊚ E16 PET Carnauba 0.50 255 12 220 282 15 ⊚ ⊚ ⊚ ⊚ C1 PET — — 255 15 220 282 15 X ⊚ ⊚ ⊚ C2 PET Carnauba 0.05 255 15 220 282 15 X ⊚ ⊚ ⊚ C3 PET Stearylstearey 0.05 255 15 220 282 15 X ⊚ ⊚ ⊚ C4 PP4) — — 160 20 — 190 17 ⊚ X — — C5 PE5) — — 110 50 — 140 19 ⊚ X — —
1)PET: Polyethylene terephthalate (Biaxial orientated film)
2)Stearylstearey: Stearic acid ester (C18-C18)
3)PET/I: Isophthalic acid copolymer polyethylene terephthalate
(Ratio of copolymerization of isophthalaic acid: 12 mol %, Biaxial oriented film)
4)PP: Polypropylene (Biaxial oriented film)
5)PE: Polyethylene
6)Wax is added to only a resin film to be an inside of can
E: Example
C: Comparative example
T.: Temperature
Claims (6)
1. A film laminated metal sheet for a container, comprising:
a metal sheet;
a resin film A laminated on a surface A of the metal sheet, the surface A being an outer surface side of the container after formation of the container;
a resin film B laminated on a surface B of the metal sheet, the surface B being an inner surface side of the container after formation of the container;
the resin film A being a thermoplastic resin film containing polyester as a main component; and
the resin film B being a thermoplastic resin film containing polyester as a main component and containing a wax component in an amount of 0.10% to 2.0% by mass with respect to the resin of the resin film B.
2. The film, laminated metal sheet according to claim 1 , wherein the wax component of the resin film B is carnauba wax or ester stearate.
3. The film laminated metal sheet according to claim 1 , wherein the resin film A and/or the resin film B is a biaxially oriented polyester film having a relaxation time T1ρof a benzene ring carbon at a 1,4 coordinate in a structure analysis according to a high solid resolution NMR is 150 msec or longer.
4. The film laminated metal sheet according to claim 1 , wherein 90 mol % or more of polyester units constituting the resin film A and/or resin film B are ethylene terephthalate units.
5. The film laminated metal sheet according to claim 1 , wherein the resin film A and/or the resin film B are constituted of at least two layers, and the difference between intrinsic viscosities of a laminate layer contacting the metal sheet and a layer other than the laminate layer is in a range of 0.01 to 0.5.
6. The film laminated metal sheet according to claim 1 , wherein the resin film B is constituted of at least two layers, and the resin film B is formed such that only an uppermost layer to be in contact with the content substance contains 0.10 to 2.0% in a ratio by mass of the wax component with respect to the resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/439,469 US20060210817A1 (en) | 1999-09-22 | 2006-05-23 | Resin film laminated metal sheet for can and method for fabricating the same |
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11-268989 | 1999-09-22 | ||
JP26898999A JP3491574B2 (en) | 1999-09-22 | 1999-09-22 | Film laminated metal plate for containers |
JP2000-074316 | 2000-03-16 | ||
JP2000074316 | 2000-03-16 | ||
JP2000-238166 | 2000-08-07 | ||
JP2000238166 | 2000-08-07 | ||
US09/665,323 US6723441B1 (en) | 1999-09-22 | 2000-09-19 | Resin film laminated metal sheet for can and method for fabricating the same |
US10/719,797 US20040101698A1 (en) | 1999-09-22 | 2003-11-20 | Resin film laminated metal sheet for can and method for fabricating the same |
US11/439,469 US20060210817A1 (en) | 1999-09-22 | 2006-05-23 | Resin film laminated metal sheet for can and method for fabricating the same |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/719,797 Division US20040101698A1 (en) | 1999-09-22 | 2003-11-20 | Resin film laminated metal sheet for can and method for fabricating the same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060210817A1 true US20060210817A1 (en) | 2006-09-21 |
Family
ID=27335690
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/665,323 Expired - Lifetime US6723441B1 (en) | 1999-09-22 | 2000-09-19 | Resin film laminated metal sheet for can and method for fabricating the same |
US10/719,797 Abandoned US20040101698A1 (en) | 1999-09-22 | 2003-11-20 | Resin film laminated metal sheet for can and method for fabricating the same |
US11/439,469 Abandoned US20060210817A1 (en) | 1999-09-22 | 2006-05-23 | Resin film laminated metal sheet for can and method for fabricating the same |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/665,323 Expired - Lifetime US6723441B1 (en) | 1999-09-22 | 2000-09-19 | Resin film laminated metal sheet for can and method for fabricating the same |
US10/719,797 Abandoned US20040101698A1 (en) | 1999-09-22 | 2003-11-20 | Resin film laminated metal sheet for can and method for fabricating the same |
Country Status (3)
Country | Link |
---|---|
US (3) | US6723441B1 (en) |
EP (2) | EP1086808B2 (en) |
DE (2) | DE60036992T3 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090041964A1 (en) * | 2005-08-12 | 2009-02-12 | Hiroshi Kubo | Laminated steel sheet for use in two-piece can and two-piece can formed of laminated steel sheet |
US20090061133A1 (en) * | 2005-08-12 | 2009-03-05 | Jfe Steel Corporation A Corporation Of Japan | Two-piece can, method for manufacturing same, and steel sheet therefor |
US20090104390A1 (en) * | 2005-08-12 | 2009-04-23 | Jfe Steel Corporation | Laminated steel sheet for two-piece can, method for manufacturing two-piece can, and two-piece laminated can |
EP2090426A1 (en) * | 2007-01-12 | 2009-08-19 | Furukawa-Sky Aluminum Corporation | Resin-coated aluminum alloy sheet material for aluminum electrolytic capacitor case, case for aluminum electrolytic capacitor, and aluminum electrolytic capacitor |
US20110220645A1 (en) * | 2008-11-25 | 2011-09-15 | Valspar Sourcing, Inc. | Packaging Articles and Lamination Films |
US10576712B2 (en) * | 2015-03-26 | 2020-03-03 | Jfe Steel Corporation | Resin-coated metal sheet for container |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6723441B1 (en) * | 1999-09-22 | 2004-04-20 | Nkk Corporation | Resin film laminated metal sheet for can and method for fabricating the same |
ATE285435T1 (en) * | 1999-12-03 | 2005-01-15 | Toray Industries | BIAXIALLY STRETCHED POLYESTER FILM FOR SHAPING |
DE10130005B4 (en) * | 2001-06-25 | 2004-12-23 | Rasselstein Gmbh | Process for coating the surface of a metal strip with a plastic film and use of a laminate produced by the process |
JP3982385B2 (en) * | 2001-11-27 | 2007-09-26 | Jfeスチール株式会社 | Resin film for laminating metal plate, method for producing the same, resin laminated metal plate and method for producing the same |
EP1449883A1 (en) * | 2003-02-18 | 2004-08-25 | Corus Technology BV | Polymer packaging layer with improved release properties |
RU2336173C2 (en) * | 2003-03-28 | 2008-10-20 | Корус Стал Б.В. | Sheet material for blanking, metal container made of such sheet material, and method of sheet material production |
AU2003284642A1 (en) * | 2003-08-18 | 2005-03-07 | Nippon Steel Corporation | Laminated metal sheet and process for producing the same |
EP1757439B1 (en) * | 2004-05-31 | 2016-07-06 | JFE Steel Corporation | Resin-coated metal plate |
DK1908583T3 (en) * | 2005-07-28 | 2015-11-09 | Jfe Steel Corp | The resin-coated metal sheet |
JP4972771B2 (en) * | 2006-12-05 | 2012-07-11 | Jfeスチール株式会社 | Method for producing aerosol drawn can and aerosol drawn can |
US9429332B2 (en) | 2010-05-25 | 2016-08-30 | 7Ac Technologies, Inc. | Desiccant air conditioning methods and systems using evaporative chiller |
CN104508417B (en) * | 2012-06-11 | 2017-03-29 | 7Ac技术公司 | For the method and system of the corrosion resistant heat exchanger of turbulence type |
US9506697B2 (en) | 2012-12-04 | 2016-11-29 | 7Ac Technologies, Inc. | Methods and systems for cooling buildings with large heat loads using desiccant chillers |
CN105121965B (en) | 2013-03-01 | 2018-05-15 | 7Ac技术公司 | Drier air conditioning method and system |
EP3614072B1 (en) | 2013-03-14 | 2022-06-22 | Emerson Climate Technologies, Inc. | Split liquid desiccant air conditioning system |
PL2969578T3 (en) * | 2013-03-14 | 2021-07-05 | Crown Packaging Technology, Inc | Ink jet printing on a metal can substrate |
EP3667191B1 (en) | 2013-06-12 | 2024-05-29 | Copeland LP | Liquid desiccant air conditioning system and method of dehumidifying and cooling an air stream in a building |
JP6674382B2 (en) | 2014-03-20 | 2020-04-01 | 7エーシー テクノロジーズ,インコーポレイテッド | Rooftop liquid desiccant system and method |
CN107110525B (en) | 2014-11-21 | 2020-02-11 | 7Ac技术公司 | Method and system for micro-fluidic desiccant air conditioning |
WO2017155099A1 (en) * | 2016-03-10 | 2017-09-14 | 新日鐵住金株式会社 | Metal sheet for container and method for manufacturing same |
CN109789672A (en) * | 2016-05-10 | 2019-05-21 | 诺维尔里斯公司 | The cover material of lamination through high annealing |
US20190116977A1 (en) * | 2017-10-24 | 2019-04-25 | Streater LLC | Cover for store shelves |
CN111373202B (en) | 2017-11-01 | 2021-11-26 | 艾默生环境优化技术有限公司 | Method and apparatus for uniform distribution of liquid desiccant in membrane modules in liquid desiccant air conditioning systems |
US10941948B2 (en) | 2017-11-01 | 2021-03-09 | 7Ac Technologies, Inc. | Tank system for liquid desiccant air conditioning system |
US11022330B2 (en) | 2018-05-18 | 2021-06-01 | Emerson Climate Technologies, Inc. | Three-way heat exchangers for liquid desiccant air-conditioning systems and methods of manufacture |
WO2020162524A1 (en) * | 2019-02-07 | 2020-08-13 | 日本製鉄株式会社 | Can lid for resin metal composite containers, which is formed of resin laminated steel sheet, can bottom for resin metal composite containers, which is formed of resin laminated steel sheet, and resin metal composite container |
WO2024062103A1 (en) * | 2022-09-23 | 2024-03-28 | Basf Se | Process for producing a composite component comprising at least one metal layer and one polymer layer |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3567486A (en) * | 1966-03-29 | 1971-03-02 | Ici Ltd | Heat-sealable film |
US4661185A (en) * | 1985-03-05 | 1987-04-28 | Signode Corporation | Method and apparatus for heat sealing strap in a strapping machine |
US4777094A (en) * | 1985-03-25 | 1988-10-11 | Moplefan S.P.A. | Polyolefinic films of improved impermeability characteristics and process for their production |
US4861647A (en) * | 1986-02-27 | 1989-08-29 | Nippon Kokan Kabushiki Kaisha | Precoating metal sheet for two-piece can |
US4956241A (en) * | 1988-12-30 | 1990-09-11 | Mobil Oil Corporation | Slip coated thermoplastic films |
US5296127A (en) * | 1986-04-25 | 1994-03-22 | Saunders William T | Composite-coated flat-rolled sheet metal manufacture |
US5424121A (en) * | 1992-09-06 | 1995-06-13 | Teijin Limited | Biaxially oriented polyester film |
US5451304A (en) * | 1991-02-26 | 1995-09-19 | Basf Lacke & Farben Ag | Process for the electrophoretic internal coating of metal containers for the storage of foodstuffs and beverages |
US5487950A (en) * | 1993-02-10 | 1996-01-30 | Wolff Walsrode Aktiengesellschaft | Multilayer lacquering of polar film substrates by a single application of material |
US5705240A (en) * | 1992-12-25 | 1998-01-06 | Toyo Seikan Kaisha, Ltd. | Coated metal plate for cans and seamless cans formed therefrom |
US5948525A (en) * | 1996-05-16 | 1999-09-07 | Toray Industries, Inc. | Biaxially stretched polyester film for forming container and method of producing the film |
US6277455B1 (en) * | 1998-01-06 | 2001-08-21 | Toyo Boseki Kabushiki Kaisha | Polyester laminate film, metal plate laminated with this film and film-laminated metal container |
US6652979B1 (en) * | 1999-12-03 | 2003-11-25 | Toray Industries, Inc. | Biaxially-oriented polyester film for fabrication |
US6723441B1 (en) * | 1999-09-22 | 2004-04-20 | Nkk Corporation | Resin film laminated metal sheet for can and method for fabricating the same |
US7198856B2 (en) * | 2001-03-14 | 2007-04-03 | Jfe Steel Corporation | Film-laminated metal sheet for container |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1471397A (en) | 1976-05-28 | 1977-04-27 | British Cellophane Ltd | Application of synthetic thermoplastic film to metal and coated metal sheets |
JPH0639146B2 (en) | 1987-03-25 | 1994-05-25 | 東洋鋼鈑株式会社 | Metal plate coated with printed polyester resin film |
GB8724244D0 (en) | 1987-10-15 | 1987-11-18 | Metal Box Plc | Producing laminated materials |
JP2835386B2 (en) | 1992-01-28 | 1998-12-14 | 東洋鋼鈑 株式会社 | Method for producing polyethylene resin-coated metal sheet excellent in hot water resistance |
EP0664209A1 (en) | 1994-01-24 | 1995-07-26 | TOYO KOHAN Co., Ltd | Metal sheet laminated with resin films |
GB2289864A (en) | 1994-05-27 | 1995-12-06 | Metal Box Plc | Laminate of metal and biaxially oriented polypropylene film |
ATE202730T1 (en) | 1997-05-02 | 2001-07-15 | Rasselstein Hoesch Gmbh | METHOD AND DEVICE FOR PLASTIC COATING OF METAL STRIP USING DIRECT EXTRUSION |
-
2000
- 2000-09-19 US US09/665,323 patent/US6723441B1/en not_active Expired - Lifetime
- 2000-09-21 EP EP20000120151 patent/EP1086808B2/en not_active Expired - Lifetime
- 2000-09-21 EP EP20070021544 patent/EP1886803B2/en not_active Expired - Lifetime
- 2000-09-21 DE DE2000636992 patent/DE60036992T3/en not_active Expired - Lifetime
- 2000-09-21 DE DE60045226T patent/DE60045226D1/en not_active Expired - Lifetime
-
2003
- 2003-11-20 US US10/719,797 patent/US20040101698A1/en not_active Abandoned
-
2006
- 2006-05-23 US US11/439,469 patent/US20060210817A1/en not_active Abandoned
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3567486A (en) * | 1966-03-29 | 1971-03-02 | Ici Ltd | Heat-sealable film |
US4661185A (en) * | 1985-03-05 | 1987-04-28 | Signode Corporation | Method and apparatus for heat sealing strap in a strapping machine |
US4777094A (en) * | 1985-03-25 | 1988-10-11 | Moplefan S.P.A. | Polyolefinic films of improved impermeability characteristics and process for their production |
US4861647A (en) * | 1986-02-27 | 1989-08-29 | Nippon Kokan Kabushiki Kaisha | Precoating metal sheet for two-piece can |
US5296127A (en) * | 1986-04-25 | 1994-03-22 | Saunders William T | Composite-coated flat-rolled sheet metal manufacture |
US4956241A (en) * | 1988-12-30 | 1990-09-11 | Mobil Oil Corporation | Slip coated thermoplastic films |
US5451304A (en) * | 1991-02-26 | 1995-09-19 | Basf Lacke & Farben Ag | Process for the electrophoretic internal coating of metal containers for the storage of foodstuffs and beverages |
US5424121A (en) * | 1992-09-06 | 1995-06-13 | Teijin Limited | Biaxially oriented polyester film |
US5705240A (en) * | 1992-12-25 | 1998-01-06 | Toyo Seikan Kaisha, Ltd. | Coated metal plate for cans and seamless cans formed therefrom |
US5487950A (en) * | 1993-02-10 | 1996-01-30 | Wolff Walsrode Aktiengesellschaft | Multilayer lacquering of polar film substrates by a single application of material |
US5948525A (en) * | 1996-05-16 | 1999-09-07 | Toray Industries, Inc. | Biaxially stretched polyester film for forming container and method of producing the film |
US6277455B1 (en) * | 1998-01-06 | 2001-08-21 | Toyo Boseki Kabushiki Kaisha | Polyester laminate film, metal plate laminated with this film and film-laminated metal container |
US6723441B1 (en) * | 1999-09-22 | 2004-04-20 | Nkk Corporation | Resin film laminated metal sheet for can and method for fabricating the same |
US6652979B1 (en) * | 1999-12-03 | 2003-11-25 | Toray Industries, Inc. | Biaxially-oriented polyester film for fabrication |
US7198856B2 (en) * | 2001-03-14 | 2007-04-03 | Jfe Steel Corporation | Film-laminated metal sheet for container |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090041964A1 (en) * | 2005-08-12 | 2009-02-12 | Hiroshi Kubo | Laminated steel sheet for use in two-piece can and two-piece can formed of laminated steel sheet |
US20090061133A1 (en) * | 2005-08-12 | 2009-03-05 | Jfe Steel Corporation A Corporation Of Japan | Two-piece can, method for manufacturing same, and steel sheet therefor |
US20090104390A1 (en) * | 2005-08-12 | 2009-04-23 | Jfe Steel Corporation | Laminated steel sheet for two-piece can, method for manufacturing two-piece can, and two-piece laminated can |
EP2090426A1 (en) * | 2007-01-12 | 2009-08-19 | Furukawa-Sky Aluminum Corporation | Resin-coated aluminum alloy sheet material for aluminum electrolytic capacitor case, case for aluminum electrolytic capacitor, and aluminum electrolytic capacitor |
US20090237864A1 (en) * | 2007-01-12 | 2009-09-24 | Osamu Kato | Resin-coated aluminum alloy sheet material for aluminum electrolytic capacitor case, case for aluminum electrolytic capacitor, and aluminum electrolytic capacitor |
EP2090426A4 (en) * | 2007-01-12 | 2009-11-18 | Furukawa Sky Aluminum Corp | Resin-coated aluminum alloy sheet material for aluminum electrolytic capacitor case, case for aluminum electrolytic capacitor, and aluminum electrolytic capacitor |
US8045321B2 (en) | 2007-01-12 | 2011-10-25 | Furukawa-Sky Aluminum Corp. | Resin-coated aluminum alloy sheet material for aluminum electrolytic capacitor case, case for aluminum electrolytic capacitor, and aluminum electrolytic capacitor |
US20110220645A1 (en) * | 2008-11-25 | 2011-09-15 | Valspar Sourcing, Inc. | Packaging Articles and Lamination Films |
US8808844B2 (en) * | 2008-11-25 | 2014-08-19 | Valspar Sourcing, Inc. | Packaging articles and lamination films |
US10576712B2 (en) * | 2015-03-26 | 2020-03-03 | Jfe Steel Corporation | Resin-coated metal sheet for container |
Also Published As
Publication number | Publication date |
---|---|
EP1086808A2 (en) | 2001-03-28 |
DE60045226D1 (en) | 2010-12-23 |
EP1086808B2 (en) | 2013-10-09 |
EP1086808B1 (en) | 2007-11-07 |
EP1886803B2 (en) | 2014-08-06 |
US6723441B1 (en) | 2004-04-20 |
EP1886803B1 (en) | 2010-11-10 |
DE60036992T3 (en) | 2014-02-06 |
EP1886803A2 (en) | 2008-02-13 |
EP1886803A3 (en) | 2008-03-26 |
DE60036992D1 (en) | 2007-12-20 |
EP1086808A3 (en) | 2002-08-07 |
DE60036992T2 (en) | 2008-08-21 |
US20040101698A1 (en) | 2004-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6723441B1 (en) | Resin film laminated metal sheet for can and method for fabricating the same | |
US10227156B2 (en) | Laminated metal sheet for two-piece can and two-piece laminated can body | |
JP5673860B2 (en) | Laminated metal plate and canned food containers | |
EP1380413A1 (en) | Film-laminated metal sheet for container | |
EP1908583B1 (en) | Resin-coated metal plate | |
EP1690675B1 (en) | Laminated metal sheet for can lid excelling in appearance after retorting | |
JP3692953B2 (en) | Film laminated metal plate for containers | |
JP4806933B2 (en) | Polyester resin laminated metal container | |
JP2003236985A (en) | Film-laminated metal sheet for container | |
JP5076385B2 (en) | Resin-coated metal plate for container and resin-coated metal can | |
WO2021131765A1 (en) | Resin-coated metal plate and resin-coated di can and manufacturing methods thereof | |
JP2006069212A (en) | Film laminated metal sheet for container | |
JP3714177B2 (en) | Film laminated metal plate for containers | |
JP3812589B2 (en) | Film laminated metal plate for containers | |
JP3780905B2 (en) | Film laminated metal plate for containers | |
JP2874582B2 (en) | Laminate and container using the same | |
JP2005161707A (en) | Resin-coated metal sheet for container and its production method | |
US20060172099A1 (en) | Metal plate coated with polyester resin, and can using the same | |
JP5050838B2 (en) | Resin-coated metal plate for containers | |
JP3029529B2 (en) | Polycarbonate resin coated metal plate | |
JP2002264258A (en) | Film-laminated metal sheet for container |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: JFE STEEL CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:JFE ENGINEERING CORPORATION;REEL/FRAME:022014/0836 Effective date: 20081218 Owner name: JFE ENGINEERING CORPORATION, JAPAN Free format text: CHANGE OF NAME;ASSIGNOR:NKK CORPORATION;REEL/FRAME:022012/0318 Effective date: 20030401 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |