WO2017098818A1 - 両面樹脂被覆容器用ラミネート鋼板 - Google Patents
両面樹脂被覆容器用ラミネート鋼板 Download PDFInfo
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- WO2017098818A1 WO2017098818A1 PCT/JP2016/081294 JP2016081294W WO2017098818A1 WO 2017098818 A1 WO2017098818 A1 WO 2017098818A1 JP 2016081294 W JP2016081294 W JP 2016081294W WO 2017098818 A1 WO2017098818 A1 WO 2017098818A1
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- resin film
- container
- resin
- steel sheet
- surface side
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/34—Coverings or external coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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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
- B32B2250/00—Layers arrangement
- B32B2250/04—4 layers
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/738—Thermoformability
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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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
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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
- B32B2439/00—Containers; Receptacles
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/66—Cans, tins
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- the present invention relates to a laminated steel sheet for a double-sided resin-coated container mainly used for a food canned container.
- solvent-type paints mainly composed of thermosetting resins have been applied to the inner and outer surfaces of metal beverage cans and food cans.
- the application of the solvent-type paint is to maintain the flavor of the contents, to prevent the corrosion of the metal that is the material of beverage cans and food canned containers, or to improve the design of the outer surface of beverage cans and food canned containers,
- the purpose was to protect the printed surface.
- solvent-based paints heat treatment at high temperature is necessary to form a coating film, and a large amount of solvent is generated during heating, so that the safety of work and the impact on the environment are affected. There was a problem.
- thermoplastic resins are excellent in processability, heat resistance, and the like, and therefore development of metal coating films based on polyester resins has been underway.
- thermoplastic resin when the thermoplastic resin is coated on the inner and outer surfaces of the container, the required properties are different between the inner surface and the outer surface, so it is necessary to properly use the thermoplastic resin.
- the melting points of the thermoplastic resins used for the inner and outer surfaces are different in manufacturing, care must be taken so that the thermoplastic resin on the low melting point side does not melt and adhere to a roll or the like.
- thermoplastic resin used for the inner surface of the container is required to have corrosion resistance to the contents (content resistance) and adhesion when in contact with the contents for a long time.
- thermoplastic resin used on the outer surface of the container the cyclic trimer in the thermoplastic resin precipitates on the resin surface during high-temperature sterilization treatment such as retort sterilization treatment, and the designability is impaired.
- high-temperature sterilization treatment such as retort sterilization treatment
- problems such as the occurrence of a phenomenon (whitening phenomenon) in which the thermoplastic resin layer itself is discolored so as to become cloudy white during the retort sterilization treatment.
- Patent Document 1 discloses that 30 to 50% by mass of polyester having ethylene terephthalate as a main repeating unit and 50 to 70% polyester having butylene terephthalate as a main repeating unit on the outer surface side of the container.
- blended by the ratio of the mass% is described. According to this metal plate, the resin film is crystallized using the heat of the retort sterilization treatment by setting the shortest half crystallization time to 100 seconds or less, and the resin film is whitened (whitened) by increasing the crystallization speed. It can be prevented from occurring.
- this metal plate has a polyester resin layer having a two-layer structure on the inner surface side of the container, and the upper polyester resin layer contains polyethylene terephthalate or 6 mol% or less of isophthalic acid as an acid component. It is also described that it is a copolymerized polyethylene terephthalate copolymerized at a ratio of In addition, the upper polyester resin layer contains 0.1 to 5% by mass of an olefin wax, and the lower polyester resin layer is a copolymer obtained by copolymerizing isophthalic acid as an acid component at a ratio of 10 to 22 mol% or less. It is also described that it is polyethylene terephthalate. Similarly, Patent Documents 2 to 5 describe techniques for improving the whitening resistance of the resin film on the outer surface side of the container.
- Patent Document 6 discloses a polyester composition containing 30 to 50% by mass of a polyester having ethylene terephthalate as a main repeating unit and 50 to 70% by mass of a polyester having butylene terephthalate as a main repeating unit. According to this polyester composition, discoloration during retort sterilization treatment can be suppressed. Patent Document 6 also describes a technique for melting the interface between the resin film and the metal plate when the melting point of the resin film is specified and the resin film is thermally fused. Patent Documents 7 and 8 describe a technique for suppressing discoloration during retort sterilization.
- Patent Documents 9 and 10 disclose steel plates in which different films are laminated on the inner surface of the can and the outer surface of the can. Further, in Patent Document 9, a polyester film having a contact angle of 70 to 120 ° is used on the inner surface side of the container, and a polyethylene terephthalate-polybutylene terephthalate having a crystallization temperature of 120 ° C. or less is used on the outer surface side of the container. A technique for improving whitening resistance by bonding (PET-PBT) is described. Patent Document 10 discloses a technique of laminating PET-PBT on the outer surface of the can and copolymerized PET on the inner surface of the can.
- PET-PBT polyethylene terephthalate-polybutylene terephthalate having a crystallization temperature of 120 ° C. or less
- JP 2005-342911 A Japanese Patent Laid-Open No. 5-331302 JP 2000-313755 A JP 2001-335682 A JP-A-6-155660 Japanese Patent Laid-Open No. 10-110046 Japanese Patent Application Laid-Open No. 09-012743 JP 07-145252 A JP 2004-168365 A JP 2014-166856 A
- Patent Document 9 does not disclose or suggest a method for simultaneously laminating different films on the outer surface side and the inner surface side. Furthermore, the technique described in Patent Document 10 adjusts the copolymerization ratio so that the melting points of the outer surface side and inner surface side films are both within the range of 220 to 256 ° C., and the outer surface side and inner surface with different melting points. It does not disclose or suggest a method of laminating side films simultaneously.
- the present invention has been made in order to solve the above-mentioned problems, and its purpose is to provide a stable supply without any trouble in manufacturing, excellent design of the appearance after retort sterilization treatment, and resistance to contents.
- the object is to provide an excellent laminated steel sheet for a double-sided resin-coated container.
- the inventors of the present invention have made extensive studies on the combination of the resin film on the inner and outer surfaces of the container and the crystallization behavior thereof, and can solve the above problems by controlling the crystallization behavior of the resin film on the inner and outer surfaces of the container. I found out.
- the laminated steel sheet for a double-sided resin-coated container conceived from the above knowledge is a steel sheet, a first polyester resin layer formed on the surface of the steel sheet that becomes the inner surface side of the container after container molding, and after container molding
- a second polyester resin layer formed on the surface of the steel sheet which is the outer surface side of the container, and the first polyester resin layer has a polyethylene terephthalate content of 95% by weight or more and a crystallinity. Is in the range of 3% to 25%, and the second polyester resin layer is composed of polyethylene terephthalate and polybutylene terephthalate, and the ratio of polybutylene terephthalate is in the range of 40% by weight to 80% by weight. It is characterized by being.
- the laminated steel sheet for a double-sided resin-coated container according to the present invention is characterized in that, in the above invention, the crystallization temperature of the second polyester resin layer is in the range of 60 ° C. or more and 72 ° C. or less.
- a laminated steel sheet for a double-sided resin-coated container which can be stably supplied without any manufacturing trouble, has an excellent design after appearance of retort sterilization, and has excellent content resistance.
- FIG. 1 is a diagram for explaining a method of heat-sealing a resin film applied to the present invention.
- the crystallization temperature of the resin film is calculated by performing thermal analysis (Differential Scanning Calorimetry: DSC) of the resin film within a temperature range of ⁇ 50 ° C. to 290 ° C. At this time, the temperature rise rate of the resin film was 10 ° C./min, and thermal analysis was performed in a nitrogen atmosphere (50 mL / min).
- DSC Different Scanning Calorimetry
- the metal plate used as the base of the laminated steel plate for double-sided resin-coated containers according to the present invention can be a steel plate that is widely used as a food can container material.
- tin-free steel hereinafter referred to as TFS
- TFS tin-free steel
- the amount of adhesion of the metal chromium and chromium hydroxide layers of TFS is not particularly limited, but from the viewpoint of workability and corrosion resistance, the amount of adhesion of the metal chromium layer is 70 to 200 mg / m 2 and the amount of adhesion of the chromium hydroxide layer is It is desirable to be within the range of 10-30 mg / m 2 .
- the resin film to be heat-sealed needs to have a polyethylene terephthalate content of 95% by weight or more and a crystallinity in the range of 3 to 25%.
- the resin film to be heat-sealed is composed of polyethylene terephthalate and polybutylene terephthalate, and the ratio of polybutylene terephthalate is in the range of 40 to 80% by weight. Further, the crystallization temperature of the resin film needs to be in the range of 60 to 72 ° C.
- the crystallinity of the resin film on the inner surface side needs to be in the range of 3 to 25%.
- the degree of crystallinity is less than 3%, there are many non-oriented layers, and spherulite growth occurs when a thermal history is received in a can or the like, so that the can-making ability is impaired.
- the degree of crystallinity exceeds 25%, the orientation layer increases and the can-making ability is impaired.
- the crystallinity of the resin film on the inner surface side is more preferably in the range of 10 to 20%.
- the crystallization temperature is in the range of 60 to 72 ° C.
- the crystallization temperature is less than 60 ° C., it is necessary to apply heat at the time of heat fusion, and the manufacturability may be impaired.
- the crystallization temperature exceeds 72 ° C., the progress of crystallization is delayed, and the whitening resistance is impaired.
- the crystallization temperature of the resin film on the outer surface side is more preferably in the range of 60 to 70 ° C.
- the steel plate 1 is heated to a predetermined temperature or higher in a heating device 11, and thereafter, is pressed on both surfaces of the steel plate 1 by a pressure-bonding roll (hereinafter referred to as a lami roll) 12.
- the resin film 2 is heat-sealed by pressing the resin film 2 (2a, 2b). Then, after the resin film 2 is heat-sealed, the steel plate 1 is cooled by the cooling device 13.
- the temperature of the steel sheet 1 at the start of heat fusion is preferably in the range of +5 to + 40 ° C. with respect to the melting point of the resin film 2.
- it is necessary to heat the polyester resin at the adhesion interface By setting the temperature of the steel plate 1 to a temperature range of + 5 ° C. or higher based on the melting point of the resin film 2, the resin in each layer is thermally fluidized, the wettability at the interface is mutually good, and excellent adhesion is achieved. Obtainable.
- the temperature of the steel sheet 1 at the start of heat-sealing is preferably + 40 ° C. or less based on the melting point of the resin film 2 because there is a concern that problems such as transfer of objects occur.
- the heat history received by the resin film 2 at the time of heat fusion is not less than the melting point of the resin film 2 and the time in contact with the steel sheet 1 is not less than 5 msec. This is because the wettability at the interface between the steel plate 1 and the resin film 2 becomes good. While in contact with the steel plate 1, the resin film 2 is melted from the vicinity of the interface with the steel plate 1 by heat. Since the thermal conductivity of the resin film 2 is extremely small, the surface layer of the resin film 2 does not reach the melting point in a time of about 5 to 40 msec. However, when this time is increased, the temperature rises to a temperature close to the melting point. There is a concern of welding to the lami roll 12. Also from this viewpoint, the thermal history received by the resin film 2 at the time of heat fusion is preferably 40 msec or less, and more preferably within the range of 10 to 25 msec.
- the lami roll 12 shown in FIG. 1 is an internal water cooling type, and it can suppress that the resin film 2 is heated too much by letting cooling water pass inside. Furthermore, since the thermal history of the resin film 2 can be controlled by changing the temperature of this cooling water independently for each of the inner and outer resin films 2, it is preferable. In this case, since the resin film 2 on the inner surface side has a higher melting point, it is preferable to set the temperature of the Lami roll 12 higher and set the temperature of the Lami roll 12 on the outer surface side lower.
- the temperature of the inner side lami roll 12 is 120 ° C. and the temperature of the outer side lami roll 12 is 80 ° C.
- the temperature of the lami roll 12 is preferably adjusted appropriately within the range of 50 to 130 ° C.
- the pressure of the lami roll 12 is preferably in the range of 9.8 to 294 N / cm 2 (1 to 30 kgf / cm 2 ) as the surface pressure.
- the pressure of the lami roll 12 is less than 9.8 N / cm 2 , even if the temperature at the start of heat fusion is + 5 ° C. or higher with respect to the melting point of the resin film 2, Since the force which spreads the resin film 2 on one surface is weak, sufficient coverage cannot be obtained. As a result, there is a possibility of affecting performance such as adhesion and corrosion resistance (content resistance).
- the pressure of the Lami roll 12 is preferably in the range of 9.8 to 294 N / cm 2 .
- the resin film 2 on the outer surface side is composed of polyethylene terephthalate and polybutylene terephthalate, and the ratio of polybutylene terephthalate (PBT) is in the range of 40 to 80% by weight.
- PBT polybutylene terephthalate
- the ratio of PBT is less than this range, it is not preferable because whitening occurs during the retort sterilization treatment. The whitening during the retort sterilization process will be described later.
- the ratio of PBT is larger than this range, the adhesion and the like deteriorate due to heating in a steam atmosphere, which is not preferable.
- the composition of the resin film 2 on the inner surface side is 95% by weight or more of polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- other components including a copolymerization component are mixed in and eluted into the content, and the content resistance is deteriorated.
- fusing point falls by addition of another component, and heat fusion property (adhesion) with a steel plate deteriorates.
- dicarboxylic acid components may be copolymerized with the material of the resin film 2 on the inner surface side and the outer surface side within a range not impairing workability, heat resistance, and corrosion resistance (inner surface side) Then, it shall be less than 5 mol%).
- dicarboxylic acid component examples include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfoisophthalic acid, aromatic dicarboxylic acid such as phthalic acid, oxalic acid, succinic acid, Examples thereof include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dimer acid, maleic acid and fumaric acid, alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and oxycarboxylic acids such as p-oxybenzoic acid.
- glycol component examples include ethylene glycol or butanediol, propanediol, pentanediol, hexanediol, neopentylglycol and other aliphatic glycols, cyclohexanedimethanol and other alicyclic glycols, bisphenol A and bisphenol S and other aromatic glycols, Examples include diethylene glycol. Two or more dicarboxylic acid components and glycol components may be used in combination.
- fluorescent brighteners, antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, pigments, antistatic agents, crystal nucleating agents, and the like can be blended.
- a disazo pigment is used for the resin film on the outer surface side, it has excellent transparency, strong coloring power, and excellent spreadability, so that a bright appearance can be obtained even after canning.
- the content is preferably 30 PHR or less.
- the addition amount of the pigment is a ratio (external ratio to the resin amount) with respect to the resin layer to which the pigment is added (when added to the lower resin layer, with respect to the lower resin layer).
- the disazo pigment at least one of pigment yellow 12, 13, 14, 16, 17, 55, 81, 83, 180, and 181 is used as the color index (CI registered name). It can.
- the molecular weight is large and the solubility in PET resin is poor from the viewpoints of vividness of color tone (bright color) and bleeding resistance in retort sterilization environment (inhibition ability against the phenomenon that pigment is deposited on the film surface).
- C. A pigment having a benzimidazolone structure having a molecular weight of 700 or more is desirable.
- I. Pigment Yellow 180 is more preferably used.
- the resin material forming the resin film 2 is not limited by the manufacturing method.
- the resin material can be formed using the following methods (1), (2), and the like.
- additives such as a fluorescent brightener, an antioxidant, a heat stabilizer, an ultraviolet absorber, and an antistatic agent may be added as necessary.
- the polyester resin used in the present invention desirably has a weight average molecular weight in the range of 5000 to 100,000, more preferably in the range of 10,000 to 80,000, from the viewpoint of improving mechanical properties, laminating properties, and taste properties.
- the thickness of the polyester resin of the present invention is preferably in the range of 5 to 50 ⁇ m, more preferably 8 to 30 ⁇ m, particularly preferably 10 to 25 ⁇ m.
- the resin film in the vicinity of the interface with the steel sheet melted by the contact with the heated steel sheet is an amorphous resin that is mechanically soft and highly deformable even after cooling and solidification, and is easily deformed and has air bubbles. It is thought that it is easy to form.
- the resin film located on the outer surface side of the container is excellent in the design of the appearance after the retort sterilization treatment with respect to the steel sheet.
- the resin film located on the inner surface side of the sheet is excellent in resistance to contents, and can retain the adhesiveness even if the retort sterilization treatment is performed in contact with the contents.
- a steel sheet having a thickness of 0.18 mm and a width of 977 mm subjected to cold rolling, annealing, and temper rolling was first degreased, pickled, and then subjected to chrome plating treatment to obtain a chromium plated steel sheet (TFS).
- a chromium plated steel sheet TFS
- the steel plate was subjected to electrolytic treatment with a chemical conversion treatment solution containing CrO 3 , F ⁇ after chromium plating in a chromium plating bath containing CrO 3 , F ⁇ , SO 4 2 ⁇ and intermediate rinsing.
- the chrome-plated steel sheet was heated with a metal band heating device using a laminating apparatus, and a resin film was heat-sealed on both sides of the chrome-plated steel sheet with a lami roll to produce a laminated steel sheet for a double-sided resin-coated container.
- the lami roll was an internal water cooling type, and the cooling water was forcibly circulated during heat fusion, thereby cooling the steel sheet while the resin film was thermally fused.
- the properties of the laminated steel sheet for a double-sided resin-coated container produced by the above method were measured and evaluated by the following methods (1) to (5). Table 1 below shows the characteristics of the heat-fused resin film and the evaluation results of the characteristics of the laminated steel sheet for a double-sided resin-coated container.
- Retort whitening resistance The retort whitening resistance of the resin film on the outer surface side was evaluated. Specifically, after filling a canned food container with tap water at room temperature, the lid was wrapped and sealed. Thereafter, the canned food container was placed in a steam retort sterilization furnace with the bottom facing down, and retort sterilization was performed at 125 ° C. for 30 minutes. After the retort sterilization treatment, the appearance change on the bottom outer surface side of the food canned container was visually observed, and retort whitening resistance was evaluated according to the following ratings.
- Adhesion wet adhesion
- a flat plate sample width 15 mm, length 120 mm
- a part of the resin film was peeled off from the long side end of the cut out sample.
- the peeled resin film was opened in a direction opposite to the peeled direction (angle: 180 °), a 50 g weight was fixed, and a retort sterilization treatment (125 ° C., 30 minutes) was performed.
- the peel length of the resin film after the retort sterilization treatment was measured, and the film wet adhesion before molding (secondary adhesion) was evaluated as the adhesion of the resin film according to the following rating.
- a laminated steel sheet for a double-sided resin-coated container which can be stably supplied without any manufacturing trouble, has an excellent design after appearance of retort sterilization, and has excellent content resistance.
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- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Wrappers (AREA)
Abstract
Description
まず、本発明における樹脂フィルムの結晶化度の算出方法について説明する。本発明では、JISで規定された密度勾配管法を用いて樹脂フィルムの密度dを測定し、測定された密度dを以下に示す数式(1)に代入することによって得られる値を樹脂フィルムの結晶化度として算出した。
次に、本発明における樹脂フィルムの結晶化温度の算出方法について説明する。本発明では、-50℃から290℃の温度範囲内で樹脂フィルムの熱分析(Differential Scanning Calorimetry : DSC)を行うことにより樹脂フィルムの結晶化温度を算出した。この時、樹脂フィルムの昇温速度は10℃/分とし、窒素雰囲気(50mL/分)で熱分析を行った。
本発明に係る両面樹脂被覆容器用ラミネート鋼板の下地となる金属板には、食品用缶詰容器用材料として広く使用されている鋼板を用いることができる。特に下層が金属クロム、上層がクロム水酸化物となる二層皮膜の表面処理鋼板であるティンフリースチール(以下、TFS)等が好適である。TFSの金属クロム及びクロム水酸化物層の付着量は特に限定されないが、加工性や耐食性の観点から、金属クロム層の付着量は70~200mg/m2、クロム水酸化物層の付着量は10~30mg/m2の範囲内とすることが望ましい。
本発明に係る両面樹脂被覆容器用ラミネート鋼板において、鋼板の2つの面のうち、両面樹脂被覆容器用ラミネート鋼板から食品用缶詰容器が成形された際に食品用缶詰容器の内面側となる面に熱融着される樹脂フィルムは、ポリエチレンテレフタレートの含有率が95重量%以上、且つ、結晶化度が3~25%の範囲内にある必要がある。
本発明に係る両面樹脂被覆容器用ラミネート鋼板において、鋼板の2つの面のうち、両面樹脂被覆容器用ラミネート鋼板から食品用缶詰容器が成形された際に食品用缶詰容器の外面側となる面に熱融着される樹脂フィルムは、ポリエチレンテレフタレートとポリブチレンテレフタレートから構成され、ポリブチレンテレフタレートの比率が40~80重量%の範囲内にある。また、樹脂フィルムの結晶化温度が60~72℃の範囲内にある必要がある。
(2)ジメチルテレフタレート、エチレングリコール、及び共重合成分をエステル交換反応させ、次いで得られる反応生成物を重縮合反応させて共重合ポリエステルとする方法。
樹脂フィルムを熱融着させた鋼板を用いて製造された食品用缶詰容器に対してレトルト殺菌処理を行なうと、多くの場合、外面側の樹脂フィルムが白化する現象が見られる。これは、外面側の樹脂フィルム内に微細な気泡が形成され、微細な気泡によって光が散乱された結果、白く濁った外観を呈するためである。加えて、外面側の樹脂フィルムに形成される微細な気泡は以下のような特徴を有する。第1に、微細な気泡は、食品用缶詰容器を乾熱環境下で加熱しても形成されない。第2に、食品用缶詰容器に内容物を充填せずに空き状態のままレトルト殺菌処理を行っても微細な気泡は形成されない。第3に、微細な気泡は外面側の樹脂フィルムの厚み方向全域に亘って観察されるわけではなく、鋼板に接している界面近傍においてのみ観察される。以上の特徴から、レトルト殺菌処理に伴う外面側の樹脂フィルムにおける微細な気泡の形成は、以下のメカニズムによって起こると考えられる。
外面側の樹脂フィルムの耐レトルト白化性を評価した。具体的には、食品用缶詰容器内に常温の水道水を満たした後、蓋を巻き締めて密閉した。その後、底部を下向きにして食品用缶詰容器を蒸気式レトルト殺菌炉の中に配置し、125℃、30分間、レトルト殺菌処理を行った。レトルト殺菌処理後、食品用缶詰容器の底部外面側の外観変化を目視で観察し、以下の評点に従って耐レトルト白化性を評価した。
◎:外観変化なし
○:外観にかすかな曇り(フィルム表面積の5%未満)発生
△:外観にかすかな曇り(フィルム表面積の5%以上10%未満)発生
×:外観が白濁(フィルム表面積の10%以上で白化発生)
両面樹脂被覆容器用ラミネート鋼板の製缶前の平板サンプル(幅15mm、長さ120mm)を切り出し、切り出されたサンプルの長辺側端部から樹脂フィルムの一部を剥離した。剥離された樹脂フィルムを剥離された方向とは逆方向(角度:180°)に開き、50gの重りを固定して、レトルト殺菌処理(125℃、30分)を行った。レトルト殺菌処理後の樹脂フィルムの剥離長さを測定し、樹脂フィルムの密着性として成形前フィルム湿潤密着性(2次密着性)を以下の評点に従って評価した。
◎:10mm未満
○:10mm以上、20mm未満
×:20mm以上
両面樹脂被覆容器用ラミネート鋼板にワックスを塗布後、直径200mmの円板を打ち抜き、絞り比2.00で浅絞り缶を得た。次いで、浅絞り缶に対して絞り比2.50で再絞り加工を行い、常法に従ってドーミング成形を行った後、トリミングし、ネックイン-フランジ加工を施すことによって深絞り缶を成形した。このようにして得た深絞り缶のネックイン部に着目し、樹脂フィルムの損傷程度を目視監察した。評価対象は深絞り缶の内外面とした。
◎:成形後の樹脂フィルムに損傷が認められない状態
○:成形後の樹脂フィルムにわずかな損傷が認められる状態
×:深絞り缶が破胴し、成形が不可能な状態
上記(1)と同様に溶接缶胴に蓋巻き締めを行い、食品用缶詰容器(内容量180ml)を作製した。その後、食品用缶詰容器に水道水を充填、缶上部に蓋を巻き締め密封し、レトルト殺菌処理(125℃、30分間)を行った。レトルト殺菌処理後に缶体が室温になってから、食品用缶詰容器上部の蓋を開け、缶体に電解液電解液(NaCl1%溶液)を50ml注入し、缶体と電解液との間に6Vの電圧を付加した。この時に測定される電流値を評価した。以下の評点に従って、耐内容物性として、蓋内面側の樹脂フィルムの被覆性を評価した。
◎:0.01mA以下
○:0.01mA超、0.1mA以下
△:0.1mA超、1mA以下
×:1mA超
上述の通りに、両面樹脂被覆容器用ラミネート鋼板の製造を行い、ラミロール等への樹脂フィルムの付着有無を観察し、以下の評点に従って製造性を評価した。
○:フィルム付着無し
×:フィルム付着有り
2a,2b 樹脂フィルム
11 加熱装置
12 圧着ロール(ラミロール)
13 冷却装置
Claims (2)
- 鋼板と、
容器成形後に容器の内面側になる前記鋼板の表面に形成された第1のポリエステル樹脂層と、
容器成形後に容器の外面側になる前記鋼板の表面に形成された第2のポリエステル樹脂層と、を備え、
前記第1のポリエステル樹脂層は、ポリエチレンテレフタレートの含有率が95重量%以上、且つ、結晶化度が3%以上25%以下の範囲内にあり、
前記第2のポリエステル樹脂層は、ポリエチレンテレフタレートとポリブチレンテレフタレートから構成され、ポリブチレンテレフタレートの比率が40質量%以上80重量%以下の範囲内にある
ことを特徴とする両面樹脂被覆容器用ラミネート鋼板。 - 前記第2のポリエステル樹脂層の結晶化温度が60℃以上72℃以下の範囲内にあることを特徴とする請求項1に記載の両面樹脂被覆容器用ラミネート鋼板。
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KR1020187014955A KR102088853B1 (ko) | 2015-12-09 | 2016-10-21 | 양면 수지 피복 용기용 라미네이트 강판 |
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US15/781,605 US20200262183A1 (en) | 2015-12-09 | 2016-10-21 | Laminated steel sheet for both-sided resin-coated container |
JP2017536031A JP6521076B2 (ja) | 2015-12-09 | 2016-10-21 | 両面樹脂被覆容器用ラミネート鋼板 |
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Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05331302A (ja) | 1992-06-03 | 1993-12-14 | Teijin Ltd | 金属缶蓋貼合せ被覆透明フィルム |
JPH06155660A (ja) | 1992-06-03 | 1994-06-03 | Toyo Kohan Co Ltd | 耐熱水性に優れたポリエステル樹脂被覆金属板 |
JPH07145252A (ja) | 1993-11-24 | 1995-06-06 | Teijin Ltd | 金属缶蓋貼合せ被覆透明フィルム |
JPH0912743A (ja) | 1995-06-27 | 1997-01-14 | Teijin Ltd | ポリエステルフイルム |
JPH10110046A (ja) | 1996-10-09 | 1998-04-28 | Unitika Ltd | 金属板ラミネート用ポリエステルフィルム及びその製造方法 |
JP2000313755A (ja) | 1999-04-28 | 2000-11-14 | Unitika Ltd | 金属板ラミネート用ポリエステルフィルム |
JP2001001446A (ja) * | 1999-06-23 | 2001-01-09 | Nkk Corp | 耐界面活性剤性に優れたラミネート鋼板 |
JP2001335682A (ja) | 2000-05-30 | 2001-12-04 | Unitika Ltd | 金属板ラミネート用ポリエステルフィルム |
JP2001353812A (ja) * | 2000-06-12 | 2001-12-25 | Toyo Seikan Kaisha Ltd | 樹脂被覆シームレス缶 |
JP2002331629A (ja) * | 2001-05-10 | 2002-11-19 | Toyobo Co Ltd | 金属板ラミネート用ポリエステル系フィルム、フィルムラミネート金属板および金属容器 |
JP2003025498A (ja) * | 2001-07-13 | 2003-01-29 | Kawasaki Steel Corp | 樹脂積層金属板 |
JP2003025500A (ja) * | 2001-07-12 | 2003-01-29 | Toyo Seikan Kaisha Ltd | 樹脂被覆シームレス缶 |
JP2004168365A (ja) | 2002-11-20 | 2004-06-17 | Nippon Steel Corp | 容器用金属板およびその製造方法 |
JP2005342911A (ja) | 2004-05-31 | 2005-12-15 | Jfe Steel Kk | 容器用樹脂被覆金属板 |
JP2009184262A (ja) * | 2008-02-07 | 2009-08-20 | Jfe Steel Corp | 2ピース缶体用ラミネート金属板および2ピースラミネート缶体 |
JP2014166856A (ja) | 2013-02-28 | 2014-09-11 | Jfe Steel Corp | 2ピース缶用ラミネート金属板および2ピースラミネート缶体 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4278270B2 (ja) * | 2000-03-22 | 2009-06-10 | 新日本製鐵株式会社 | フィルムラミネートツーピース缶 |
JP4142959B2 (ja) * | 2003-02-05 | 2008-09-03 | 大和製罐株式会社 | 熱可塑性樹脂被覆金属板の製造方法 |
EP1627820B1 (en) * | 2003-05-22 | 2012-06-20 | JFE Steel Corporation | Laminated steel sheet |
JP4806933B2 (ja) * | 2005-01-28 | 2011-11-02 | Jfeスチール株式会社 | ポリエステル樹脂ラミネート金属容器 |
CN103608491B (zh) * | 2011-03-25 | 2016-06-15 | 日涂表面处理化工有限公司 | 表面处理剂组合物、表面处理钢板的制造方法、表面处理钢板、有机被覆表面处理钢板、罐盖、罐体以及无缝罐 |
WO2013099563A1 (ja) * | 2011-12-26 | 2013-07-04 | Jfeスチール株式会社 | ラミネート金属板および食品用缶詰容器 |
JP5403195B1 (ja) * | 2012-04-19 | 2014-01-29 | Jfeスチール株式会社 | ラミネート金属板および食品用缶詰容器 |
-
2016
- 2016-10-21 NZ NZ742868A patent/NZ742868A/en not_active IP Right Cessation
- 2016-10-21 CA CA3006490A patent/CA3006490C/en not_active Expired - Fee Related
- 2016-10-21 KR KR1020187014955A patent/KR102088853B1/ko active IP Right Grant
- 2016-10-21 US US15/781,605 patent/US20200262183A1/en active Pending
- 2016-10-21 CN CN201680071293.XA patent/CN108367542B/zh active Active
- 2016-10-21 AU AU2016367903A patent/AU2016367903B2/en not_active Ceased
- 2016-10-21 WO PCT/JP2016/081294 patent/WO2017098818A1/ja active Application Filing
- 2016-10-21 JP JP2017536031A patent/JP6521076B2/ja active Active
- 2016-10-21 EP EP16872718.8A patent/EP3388234B1/en active Active
- 2016-10-21 MY MYPI2018702187A patent/MY174843A/en unknown
- 2016-12-05 TW TW105140090A patent/TWI611919B/zh active
-
2018
- 2018-06-05 PH PH12018550082A patent/PH12018550082B1/en unknown
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05331302A (ja) | 1992-06-03 | 1993-12-14 | Teijin Ltd | 金属缶蓋貼合せ被覆透明フィルム |
JPH06155660A (ja) | 1992-06-03 | 1994-06-03 | Toyo Kohan Co Ltd | 耐熱水性に優れたポリエステル樹脂被覆金属板 |
JPH07145252A (ja) | 1993-11-24 | 1995-06-06 | Teijin Ltd | 金属缶蓋貼合せ被覆透明フィルム |
JPH0912743A (ja) | 1995-06-27 | 1997-01-14 | Teijin Ltd | ポリエステルフイルム |
JPH10110046A (ja) | 1996-10-09 | 1998-04-28 | Unitika Ltd | 金属板ラミネート用ポリエステルフィルム及びその製造方法 |
JP2000313755A (ja) | 1999-04-28 | 2000-11-14 | Unitika Ltd | 金属板ラミネート用ポリエステルフィルム |
JP2001001446A (ja) * | 1999-06-23 | 2001-01-09 | Nkk Corp | 耐界面活性剤性に優れたラミネート鋼板 |
JP2001335682A (ja) | 2000-05-30 | 2001-12-04 | Unitika Ltd | 金属板ラミネート用ポリエステルフィルム |
JP2001353812A (ja) * | 2000-06-12 | 2001-12-25 | Toyo Seikan Kaisha Ltd | 樹脂被覆シームレス缶 |
JP2002331629A (ja) * | 2001-05-10 | 2002-11-19 | Toyobo Co Ltd | 金属板ラミネート用ポリエステル系フィルム、フィルムラミネート金属板および金属容器 |
JP2003025500A (ja) * | 2001-07-12 | 2003-01-29 | Toyo Seikan Kaisha Ltd | 樹脂被覆シームレス缶 |
JP2003025498A (ja) * | 2001-07-13 | 2003-01-29 | Kawasaki Steel Corp | 樹脂積層金属板 |
JP2004168365A (ja) | 2002-11-20 | 2004-06-17 | Nippon Steel Corp | 容器用金属板およびその製造方法 |
JP2005342911A (ja) | 2004-05-31 | 2005-12-15 | Jfe Steel Kk | 容器用樹脂被覆金属板 |
JP2009184262A (ja) * | 2008-02-07 | 2009-08-20 | Jfe Steel Corp | 2ピース缶体用ラミネート金属板および2ピースラミネート缶体 |
JP2014166856A (ja) | 2013-02-28 | 2014-09-11 | Jfe Steel Corp | 2ピース缶用ラミネート金属板および2ピースラミネート缶体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3388234A4 |
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PH12018550082A1 (en) | 2019-03-18 |
PH12018550082B1 (en) | 2019-03-18 |
JP6521076B2 (ja) | 2019-05-29 |
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NZ742868A (en) | 2018-12-21 |
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CN108367542B (zh) | 2021-03-30 |
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US20200262183A1 (en) | 2020-08-20 |
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JPWO2017098818A1 (ja) | 2017-12-07 |
TWI611919B (zh) | 2018-01-21 |
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