WO2020026803A1 - Polyester-resin-coated metal sheet, method for producing polyester-resin-coated metal sheet, and container and container lid that comprise polyester-resin-coated metal sheet - Google Patents
Polyester-resin-coated metal sheet, method for producing polyester-resin-coated metal sheet, and container and container lid that comprise polyester-resin-coated metal sheet Download PDFInfo
- Publication number
- WO2020026803A1 WO2020026803A1 PCT/JP2019/028039 JP2019028039W WO2020026803A1 WO 2020026803 A1 WO2020026803 A1 WO 2020026803A1 JP 2019028039 W JP2019028039 W JP 2019028039W WO 2020026803 A1 WO2020026803 A1 WO 2020026803A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal plate
- diffraction intensity
- ray diffraction
- polybutylene terephthalate
- polyester resin
- Prior art date
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
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
Definitions
- the present invention relates to a polyester resin-coated metal plate, a method for producing a polyester resin-coated metal plate, a container made of the polyester resin-coated metal plate, and a container lid.
- thermoplastic resin film a resin-coated metal plate in which a thermoplastic resin film is laminated on a metal plate surface is known as a material for containers such as metal cans for beverages and foods.
- thermoplastic resin film a polyester film or the like is used.
- Containers such as metal cans for beverages and foods as described above need to be able to withstand the retort sterilization performed after filling the contents.
- retort sterilization processes such as a batch process and a continuous process.
- the batch retort process includes a step of exposing a container such as a metal can to high-temperature steam for several minutes to several tens of minutes.
- the continuous retort treatment includes a step of exposing a container such as a metal can conveyed to a sterilization chamber by an endless chain conveyor into high-temperature steam for several minutes to tens of minutes.
- continuous production lines which are relatively new systems compared to the batch system, have been increasing for the purpose of improving productivity.
- thermoplastic resin film-coated metal that has the property that delamination of a film from a metal plate does not occur even under a severe retort sterilization environment such as a continuous production line with a very high temperature rise rate. Boards are in great demand.
- retort brushing (white spots) is a phenomenon in which the resin layer that has undergone the above-described retort sterilization treatment becomes partially white and impairs the appearance.
- thermoplastic resin film it is also presumed that water droplets adhering to the can lid or the bottom of the can pass through the thermoplastic resin film and become bubbles between the metal plate and the resin film.
- the water contained in the film foams inside the film when it reaches the vaporization temperature due to a sudden rise in temperature, so that the portion looks white.
- thermoplastic resin-coated metal container that can be applied to a retort pot with a particularly high heating rate, such as a continuous production line.
- thermoplastic resin film In order to improve such a problem of retort brushing (white spots), a method of using a resin in which polyethylene terephthalate (PET) is blended with polybutylene terephthalate (PBT) has been proposed as a thermoplastic resin film. Since PBT has a high crystallization rate, the film is crystallized in a short time from the start of the retort sterilization treatment, thereby suppressing water vapor transmission and suppressing the occurrence of retort brushing (white spots). It cannot be applied to applications in which the temperature of the retort kettle is extremely high, as in the production line of the formula.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- Patent Literature 1 discloses a resin-coated steel sheet for a container in which a non-oriented polybutylene terephthalate (PBT) homopolymer is coated on a steel sheet.
- PBT polybutylene terephthalate
- Patent Document 2 discloses a laminated metal plate in which a biaxially stretched polybutylene terephthalate film is laminated, for example, as a laminated metal plate for a can used as a material for a beverage can or a food can, in contact with the surface of the metal plate. I have.
- Patent Document 1 aims at improving thermal embrittlement and thermal shrinkage of a film in a coating baking process and a welding process by setting a specific polyester film in an unoriented state.
- the use of the container is not premised on the retort sterilization treatment, and its performance is not confirmed on the assumption that retort adhesion is required.
- a stretched polybutylene terephthalate film as disclosed in Patent Literature 2 has the advantage that the film strength is large by stretching and the dimensional stability is good, so that the wound shape of the film is not easily collapsed. That is, it is preferable to use a stretched film from the viewpoint of productivity, since the risk of film breakage or film wrinkling when laminating on a metal plate is reduced.
- the stretched polybutylene terephthalate film has higher crystallinity than the stretched polyethylene terephthalate film and has a large residual stress inside the film due to the oriented crystal by stretching, when the resin-coated metal plate is processed into a container or a lid, There was a problem that the film was easily peeled off during the retort sterilization treatment.
- the present inventors have solved the problem of retort brushing (white spots) under retort conditions with a very high heating rate, such as a continuous retort method, and at the same time, have improved the impact resistance and the container.
- retort adhesiveness In order to solve the moldability of the film and the container lid, and the adhesiveness of the film during the retort sterilization treatment (retort adhesiveness), intensive studies were made.
- a polyester resin-coated metal plate of the present invention has a metal plate and a polybutylene terephthalate layer laminated so as to be in contact with at least one surface of the metal plate, and the (100) plane in the polybutylene terephthalate layer
- the ratio R of the X-ray diffraction intensity to the X-ray diffraction intensity of the (1-11) plane is in the range of 1.3 or more and 6.6 or less.
- the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2 ⁇ is confirmed in the range of 23.0 ° to 24.0 °
- the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2 ⁇ is in the range of 25.0 ° to 26.0 °
- the X-ray diffraction intensity ratio R (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.)
- the different polyester resin layer is a polyethylene terephthalate resin layer, a polyethylene terephthalate resin layer in which isophthalic acid is copolymerized, or a blend of polyethylene terephthalate and polybutylene terephthalate. Or a resin layer in which polyethylene terephthalate copolymerized with isophthalic acid and polybutylene terephthalate are blended.
- the polyester resin-coated metal plate according to the above (2) or (3) it is preferable that the different polyester resin layers are laminated in a non-oriented state.
- the X-ray diffraction intensity ratio R is in a range of 1.3 or more and 3.0 or less.
- a container of the present invention is formed by using the polyester resin-coated metal plate according to any one of the above (1) to (6).
- a container lid according to the present invention is formed by using the polyester resin-coated metal plate according to any one of the above (1) to (6).
- the method for producing a polyester resin-coated metal plate according to the present invention is characterized in that the X-ray diffraction intensity of the (100) plane and the X-ray A method for producing a polyester resin-coated metal plate, comprising laminating a biaxially stretched polybutylene terephthalate film using a laminating roll so that a line diffraction intensity ratio R falls within a range of 1.3 or more and 6.6 or less.
- the plate temperature of the plate is set in the range of 240 ° C. to 300 ° C.
- the surface temperature of the laminating roll is set in the range of 30 ° C. to 180 ° C.
- the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2 ⁇ is confirmed in the range of 23.0 ° to 24.0 °
- the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2 ⁇ is in the range of 25.0 ° to 26.0 °
- the X-ray diffraction intensity ratio R (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.
- ADVANTAGE OF THE INVENTION while resolving the problem of retort brushing (white spots) at the time of retort sterilization treatment (resistance to retort brushing), impact resistance after performing severe processing such as drawing and ironing, and can production. It is possible to provide a polyester resin-coated metal plate excellent in moldability that can withstand severe processing such as drawing and ironing, and adhesion between the film and the metal plate during retort sterilization (retort adhesion). Further, according to the present invention, it is possible to provide a method for producing a polyester resin-coated metal plate, a container made of the polyester resin-coated metal plate, and a container lid.
- FIG. 3 is a view showing an X-ray diffraction peak intensity of a polybutylene terephthalate layer A of a polyester resin-coated metal plate in Example 1.
- FIG. 9 is a view showing an X-ray diffraction peak intensity of a polybutylene terephthalate layer A of a polyester resin-coated metal plate in Example 2.
- the polyester resin-coated metal plate in the present embodiment includes a metal plate 1 and a polybutylene terephthalate layer A laminated (laminated) so as to be in contact with at least one surface of the metal plate 1.
- the polybutylene terephthalate layer A is preferably provided on the outer side when the metal plate 1 is formed into a container or a container lid.
- Metal plate 1 As the metal plate 1, a known metal plate used for a container such as a normal metal can or a container lid can be used, and is not particularly limited. For example, as a metal plate that is preferably used, a surface-treated steel plate or a light metal plate such as an aluminum plate and an aluminum alloy plate can be used.
- Aluminum killed steel, low carbon steel, etc. can be used as the surface-treated steel sheet.
- tin plating, nickel plating, zinc plating, electrolytic chromic acid treatment, chromic acid treatment, non-chromium treatment using aluminum or zirconium one or more types Can be used.
- an aluminum plate and an aluminum alloy plate are used.
- the aluminum alloy plate for metal cans, for example, JIS A3000 (Al-Mn) can be used.
- JIS A5000-based Al-Mg-based
- the thickness and the like of the metal plate can be appropriately selected according to the purpose of use.
- a polybutylene terephthalate layer A is provided on at least one surface of the metal plate 1.
- the polybutylene terephthalate layer A is characterized by being composed of a homopolymer of polybutylene terephthalate (PBT). That is, the polybutylene terephthalate layer A of the present embodiment is not a blend film with polyethylene terephthalate (PET) or the like, and does not include a copolymer component such as isophthalate.
- the homopolymer of polybutylene terephthalate (PBT) in the present embodiment preferably has a melting point (Tm) of 215 ° C. to 225 ° C. and an intrinsic viscosity (IV value) of 1.15 to 1.30 dl / g. .
- additives such as a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, and a crystallization accelerator, as necessary. May be added.
- a sequential biaxial stretching method due to a high crystallization rate
- production by a simultaneous biaxial stretching method is general.
- the simultaneous biaxial stretching method include a tubular method and a tenter method, but the tubular method is particularly preferable in that the strength balance in the vertical and horizontal directions is good.
- the stretching ratio is preferably in the range of 2.7 to 4.5 times for each of MD and TD in consideration of the strength physical properties, transparency, and thickness uniformity of the film.
- the ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is in the range of 1.3 or more and 6.6 or less.
- the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2 ⁇ is confirmed in the range of 23.0 ° to 24.0 °
- the X-ray diffraction intensity of the (1-11) plane is Is the maximum value observed when the diffraction angle 2 ⁇ is in the range of 25.0 ° to 26.0 °.
- the X-ray diffraction intensity ratio R represents the value of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”. In this specification, for convenience of notation, Is described as “(1-11) plane”.
- the peak at which the diffraction angle 2 ⁇ is found in the range of 23.0 ° to 24.0 ° in X-ray diffraction is the intensity caused by the oriented crystal of PBT. This is because the benzene ring in the molecular chain of PBT is plane-oriented to the (100) plane.
- the peak observed when the diffraction angle 2 ⁇ is in the range of 25.0 ° to 26.0 ° is the diffraction intensity of the (1-11) plane.
- the (1-11) plane is a plane inclined at 45 ° with respect to the (100) plane of the film surface. Therefore, the observation of the peak derived from the (1-11) plane is considered to mean that a part of the benzene ring in the PBT is oriented at 45 ° to the film surface. .
- the peak derived from the (1-11) plane is observed in any of a homopolymer of polyethylene terephthalate (PET), a copolymer film of polyethylene terephthalate and isophthalate (PET / I), and a blend film of PET and PBT. It is not strongly observed. Therefore, the peak derived from the (1-11) plane is presumed to be a peculiar phenomenon in the PBT homopolymer.
- the meaning of defining the X-ray diffraction intensity ratio R of the (100) plane and the X-ray diffraction intensity of the (1-11) plane is as follows. As described above, it is known that the X-ray diffraction intensity of PBT appears strongly when the orientation of the benzene ring in the molecular chain is aligned with a specific plane.
- the benzene rings are aligned parallel to the film surface, so that the X-ray diffraction intensity appears on the (100) plane.
- the present inventors in the polybutylene terephthalate layer A of the polyester resin-coated metal plate, by strictly controlling the amount of the oriented crystal and the amount of the orientation return, impact resistance, moldability, retort adhesion, It has been found that favorable results are obtained in all cases.
- the ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is 1.3 or more. That is, the range of 6 or less was reached.
- the value of the X-ray diffraction intensity ratio R is set in a preferable range by a method of thermally bonding a biaxially stretched PBT film to a metal plate, but the present embodiment is limited to this example. is not. That is, if the X-ray diffraction intensity ratio R of the laminated PBT film is within the specified range by a method other than the thermal bonding, the impact resistance, moldability, retort adhesion, retort brushing resistance required by the present invention are required. , It is possible to obtain preferable characteristics.
- the peak of the X-ray diffraction intensity of the (100) plane after laminating is the X-ray diffraction of the (100) plane of the raw film before lamination. It was confirmed that an X-ray diffraction intensity peak of the (1-11) plane appeared within a range of 60% or less of the intensity peak. This is because in the region where the X-ray diffraction intensity on the (100) plane is 60% or less, the so-called “melt layer” in which the oriented crystals are completely dissolved on the contact side between the metal plate and the biaxially stretched PBT film during lamination. It is presumed that an oriented layer is formed.
- the extremely short time until the “melt layer” is rapidly cooled is obtained. It is estimated that the peak of the X-ray diffraction intensity appears on the (1-11) plane because the orientation is restored in time. Therefore, it can be said that the peak of the X-ray diffraction intensity on the (1-11) plane is a parameter linked to the change in the peak of the X-ray diffraction intensity on the (100) plane, which is an index of the oriented crystal.
- the peak of the X-ray diffraction intensity of the (1-11) plane gradually decreases, while the X-ray diffraction intensity of the (100) plane, which is an index of the oriented crystal, is larger. Shows a downward trend.
- the difference between the two peak intensities linked with each other is small and the intensity ratio is within the above-specified range, both the moldability and the retort adhesion can be achieved.
- the ratio between the X-ray diffraction intensity of the (100) plane and the X-ray diffraction intensity of the (1-11) plane had to be 6.6 or less.
- X-ray diffraction intensity is observed not only on the (100) plane but also on the (1-11) plane.
- the X-ray diffraction intensity of the (1-11) plane was such that the oriented crystals in the film were completely dissolved by heat during lamination, that is, a so-called “melt layer” was formed on the contact side between the metal plate and the film. Can be considered. Therefore, the state where a certain amount of X-ray diffraction intensity peaks can be confirmed on the (1-11) plane is considered to indicate the state where a certain amount of “melt layer” that effectively acts on the adhesion is formed. .
- the above-mentioned orientation return increases the ratio of returning to the original oriented crystal state, resulting in sufficient adhesion. May not be able to be secured. From these estimations, the peak of the X-ray diffraction intensity of the (1-11) plane is that the "melt layer" which effectively acts on the adhesion is formed in a certain amount and the amount of the orientation return after lamination is small. We thought that it could be an index to show that it was suppressed.
- the present inventors By controlling the oriented crystals in the film using the parameters based on the peak intensity in the (1-11) plane, the present inventors have achieved the required formability and retort adhesion even in the PBT single film. I thought I could. Furthermore, it was considered that both the properties of the moldability and the retort adhesion could be compatible with more preferable dimensions by the ratio of the peak intensities in both the (100) plane and the (1-11) plane.
- the X-ray diffraction intensity ratio R is less than 1.3. It is not a target.
- the above-mentioned X-ray diffraction intensity ratio R exceeds 6.6, the amount of the oriented crystal of the (100) plane is too large relative to the amount of the orientation return of the (1-11) plane.
- the ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is more preferably 1.3 or more and 3.0 or less, and 1.3 or more and 2.7 or less. Is more preferable.
- the measurement of the peak intensity in the X-ray diffraction of the polybutylene terephthalate layer A can be performed by a general resin X-ray diffraction measurement method.
- the resin-coated surface of the metal plate on which the polybutylene terephthalate layer A is formed is measured using an X-ray diffractometer.
- the sample is mounted so that the incident angle and the reflection angle of the X-ray are each ⁇ with respect to the diffraction angle 2 ⁇ , and the incident X-ray and the diffraction X-ray are symmetric with respect to the normal to the film surface.
- the X-ray diffraction spectrum is measured by scanning the diffraction angle 2 ⁇ between, for example, 10 ° and 30 ° while keeping the angle ⁇ always equal.
- background correction is not required, and the peak height of the obtained X-ray diffraction spectrum is measured without background correction.
- the polybutylene terephthalate layer A is preferably a single layer.
- the homopolymer of polybutylene terephthalate (PBT) is effective for improving the problem of retort brushing (white spots) due to its high crystallization speed. If the polybutylene terephthalate layer A is formed as a multilayer with a resin other than the PBT homopolymer, the crystallization rate of the resin layer other than the PBT homopolymer is slow and insufficient, and a sufficient water vapor barrier property cannot be secured. As a result, retort brushing (white spots) occurs in the resin layer other than the PBT homopolymer, which is not preferable.
- the thickness of the polybutylene terephthalate layer A formed on the metal plate 1 is preferably 5 to 30 ⁇ m from the viewpoint of moldability and retort adhesion during retort sterilization.
- the thickness of the polybutylene terephthalate layer A is less than 5 ⁇ m, the ratio of the metal exposed portion after molding increases, and rust is generated after retort sterilization.
- the thickness of the polybutylene terephthalate layer A exceeds 30 ⁇ m, the residual stress in the film is too large, which makes it difficult to ensure retort adhesion and is undesirable from the viewpoint of cost.
- the polyester resin-coated metal plate in the present embodiment includes the metal plate 1 and the polybutylene terephthalate layer A laminated so as to be in contact with at least one surface of the metal plate 1 as described above.
- the polybutylene terephthalate layer A may be laminated on both sides of the metal plate 1 as shown in FIG. As shown in FIG. 2B, a polybutylene terephthalate layer A is laminated on one surface of the metal plate 1, and a polyester resin layer B different from the polybutylene terephthalate layer A is laminated on the other surface. May be.
- the thickness of the resin layer and the thickness of the metal plate are schematically illustrated for the sake of convenience, and thus are different from the exact thickness ratio.
- the polyester resin layer B will be described.
- polyester resin layer B examples include polyethylene terephthalate resin, polyethylene terephthalate / isophthalate resin in which isophthalic acid is copolymerized, resin in which polyethylene terephthalate and polybutylene terephthalate are blended, and polyethylene in which isophthalic acid is copolymerized.
- the resin examples include a resin in which terephthalate / isophthalate and polybutylene terephthalate are blended.
- the invention is not limited thereto, and a known polyester resin can be applied.
- the polyester resin layer B is laminated in an unoriented state from the viewpoint of ensuring moldability and retort adhesion in a container having high molding difficulty, for example, a DI (Drawing & Ironing) can. Further, the polyester resin layer B may be a single layer or a multilayer.
- polyester resin layer B can be blended with known additives, for example, an antiblocking agent, a pigment, an antistatic agent, an antioxidant, a lubricant and the like by a known formulation.
- the polyester resin-coated metal plate of the present embodiment can be manufactured by forming a polybutylene terephthalate layer A on at least one surface of the metal plate 1 by thermal bonding.
- the method for producing a polyester resin-coated metal sheet according to the present embodiment is characterized in that the X-ray diffraction intensity of the (100) plane and the X-ray
- a method for producing a polyester resin-coated metal sheet, comprising laminating a biaxially stretched polybutylene terephthalate film using a laminating roll so that a diffraction intensity ratio R falls within a range of 1.3 or more and 6.6 or less. Is characterized by having the following steps. (1) The temperature of the metal plate is set within a range of 240 ° C. to 300 ° C., the surface temperature of the laminating roll is set within a range of 30 ° C. to 180 ° C.
- the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2 ⁇ is found in the range of 23.0 ° to 24.0 °
- the X-ray diffraction intensity of the (1-11) plane is The diffraction angle 2 ⁇ is the maximum value observed in the range of 25.0 ° to 26.0 °
- the X-ray diffraction intensity ratio R (100) plane diffraction intensity / (1-11) plane diffraction intensity. is there.
- the laminating step will be described.
- the metal plate 1 is heated to a temperature of 240 ° C. to 300 ° C. by a heating roll (not shown). Then, the heated metal plate 1 is supplied between the laminating rolls 3A and 3B.
- the heating temperature of the metal plate 1 is lower than 240 ° C.
- the X-ray diffraction intensity of the (100) plane of the biaxially stretched PBT film remaining after the formation of the polybutylene terephthalate layer A that is, the amount of oriented crystals is reduced. Since it is too large, it is difficult to make the value of the X-ray diffraction intensity ratio R within a preferable range, which is not preferable.
- the heating temperature of the metal plate 1 exceeds 300 ° C.
- the polybutylene terephthalate layer A is laminated, the whole film is in a molten state and is welded to the laminating roll or the surface of the laminating roll is rough. It is not preferable because the degree is transferred.
- the polybutylene terephthalate film A ′ for forming the polybutylene terephthalate layer A is rewound from the supply roll, and supplied between the laminate rolls 3A and 3B so as to contact one surface of the metal plate 1.
- the metal plate 1 and the polybutylene terephthalate film A ' are sandwiched between the laminating rolls 3A and 3B to form a polyester resin-coated metal plate.
- a known roll can be used as the laminating roll.
- Known rolls include, for example, fluororubber rolls and silicone rubber rolls.
- the diameter of the laminating roll is not particularly limited, a laminating roll having a diameter of, for example, 200 mm to 550 mm can be used.
- the surface temperature of the laminating roll is controlled to a predetermined temperature by a cooling roll or a heating roll (not shown).
- the temperature is preferably set to 30 ° C. to 180 ° C. in a preferable range of the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A. It is preferable to set it within.
- the laminating speed for producing the polyester resin-coated metal sheet is not particularly limited, but is generally preferably 50 mpm to 300 mpm.
- the laminating speed is related to the transit time of the nip portion of the laminating roll. That is, when the laminating speed is high, the passing time of the nip is short, and when the laminating speed is low, the passing time of the nip is long. That is, the passage time of the nip portion is a time during which the polyester resin-coated metal plate is cooled by the laminating roll. Therefore, it can be said that the laminating speed is one of the parameters for controlling the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A.
- the laminating speed is less than 50 mpm, it is not preferable because the time during which the film receives radiant heat from the metal plate immediately before sticking becomes longer and the film wrinkles easily occur.
- the laminating speed exceeds 300 mpm, the amount of air bubbles caught between the metal plate and the film increases significantly, which is not preferable from the viewpoint of corrosion resistance and retort adhesion.
- the polybutylene terephthalate film A ′ is preferably biaxially stretched by a general method as described above.
- the degree of biaxial orientation of the biaxially stretched film is not particularly limited.
- a resin layer may be formed by simultaneously laminating films on both surfaces of the metal plate 1.
- the polybutylene terephthalate layer A may be formed on both surfaces of the metal plate 1.
- a polybutylene terephthalate layer A may be formed on one side of the metal plate 1 and a polyester resin layer B different from the polybutylene terephthalate layer A may be provided on the other side.
- the polyester resin film B ′ to be the polyester resin layer B can be sandwiched between the laminating rolls 3A and 3B in the same manner as the polybutylene terephthalate film A ′ and thermally bonded.
- a quench tank 12 containing cooling water is provided below the laminating rolls 3A and 3B.
- the obtained polyester resin-coated metal sheet is sent to the quench tank 12.
- the oriented crystals in the polybutylene terephthalate resin layer A are dissolved by the heat in the laminating step.
- the collapsed oriented crystal loses its original orientation until the obtained polyester resin-coated metal plate is sent to the quench tank 12. A phenomenon of returning to the crystalline state occurs (orientation return).
- the time T at which the orientation is returned is defined as the time from immediately after lamination to the time when the cooling water of the quench tank enters. More specifically, as shown in FIG. 3, the Y from the point X immediately after the arbitrary point P of the polyester resin-coated metal plate has come out of the nip portion of the laminating roll to the point at which the cooling water of the quench tank 12 enters is removed. Defined as the time required to move to a point.
- the time T during which the alignment return occurs is 3 seconds or less. If the time T during which the orientation return occurs exceeds 3 seconds, the above-described orientation return becomes too large, and it becomes difficult to control the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, to a preferable value. Therefore, in the present embodiment, it can be said that the time T is preferably set to 3 seconds or less.
- the quench tank 12 containing cooling water is provided below the laminating rolls 3A and 3B, as shown in FIG.
- the obtained polyester resin-coated metal sheet is sent to the quench tank 12 and immediately quenched to 80 ° C. or less, in order to control the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, to a preferable value. Is preferred. If the cooling temperature is higher than 80 ° C., the orientation return proceeds even after cooling, and the value of the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, may not be able to be controlled to a preferable range. Absent.
- the temperature of the metal plate 1 before the thermal bonding (b) the surface temperature of the laminating roll, (c) the cooling time at the laminating roll nip portion, and (d) the orientation return occurs.
- the state of the oriented crystal of the polybutylene terephthalate layer A is controlled by setting each parameter of the time T to an optimum value.
- a container such as a metal can in this embodiment will be described.
- the container in the present embodiment include, but are not limited to, metal cans such as beverage cans and food cans, square cans, cans, drums, battery cases, and pouches.
- the container of the present embodiment is manufactured by a known can manufacturing method using the above-described polyester resin-coated metal plate.
- Known methods for making cans include, for example, drawing, drawing and ironing, stretch draw and ironing, and the like.
- the above-mentioned polybutylene terephthalate layer A is formed on the outer surface from the viewpoint of suppressing the occurrence of retort brushing (white spots).
- the polybutylene terephthalate layer A may be laminated on both the outer surface and the inner surface of the container.
- the above-mentioned polybutylene terephthalate layer A may be formed on the outer surface of the container, and the above-mentioned polyester resin layer B may be laminated on the inner surface.
- Container lid examples of the container lid in the present embodiment include a so-called stay-on-tab type SOT can lid and a full open type easy open can lid (EOE). Alternatively, a three-piece can roof can be mentioned. These can lids can also be manufactured by a known method.
- the above-mentioned polybutylene terephthalate layer A is formed on the outer surface from the viewpoint of suppressing the occurrence of retort brushing (white spots).
- polybutylene terephthalate layer A may be laminated on the outer and inner surfaces of the container lid.
- a polyester resin layer B may be laminated on the inner surface of the container lid, or a coating film (not shown) may be formed.
- a tin-free steel (TFS) plate having a thickness of 0.225 mm was used as the metal plate.
- Example 1 As the polybutylene terephthalate layer A, a biaxially stretched polybutylene terephthalate film (trade name: BOBLET) having a thickness of 15 ⁇ m from Kojin Film & Chemicals Co., Ltd. was prepared.
- BOBLET biaxially stretched polybutylene terephthalate film
- BOBLET 15 ⁇ m made by Kojin Film & Chemicals Co., Ltd. was brought into contact with both sides of a metal plate heated to 260 ° C., sandwiched between a pair of laminating rolls, pressed and laminated, and coated with a polyester resin.
- a metal plate was produced.
- a roll made of fluororubber was used as a laminating roll, and its surface temperature was 180 ° C.
- the laminating speed was 55 mpm (meter @ per @ minute).
- the obtained polyester resin-coated metal plate was immediately sent to a quench tank containing cooling water and cooled.
- the temperature of the cooling water was 50 ° C
- the temperature of the polyester resin-coated metal plate after cooling in the quench tank was 50 ° C.
- the time T during which the alignment return occurred was 3 seconds.
- the X-ray diffraction intensity ratio of the polybutylene terephthalate layer A of the obtained polyester resin-coated metal plate was calculated.
- the measurement conditions of X-ray diffraction were as follows.
- X-ray diffractometer RINT-2500, manufactured by Rigaku Corporation
- Tube voltage 40kV
- Tube current 200mA
- Divergence slit 1/2 °
- Light receiving slit 0.15mm
- FIG. 4 shows the obtained X-ray diffraction spectrum.
- the background correction was not performed (the same applies to other examples and comparative examples).
- a paraffin wax is applied to the polyester resin-coated metal plate obtained as described above at a rate of 50 mg / m 2 on one side, and the polybutylene terephthalate layer A is applied to a disk (blank) having a diameter of 142 mm so as to be the outer surface of the can.
- a 1st cup was prepared by drawing. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
- Ion-exchanged water was put into the obtained cup up to the upper end, and a retort sterilization treatment was performed at 125 ° C. for 45 minutes.
- the dents were provided at three locations: the rolling direction of the sheet, the 45 ° direction, and the perpendicular direction. Thereafter, the ERV (Enamel Rate Value) of the dent portion was measured.
- a solution obtained by diluting a specified electrolytic solution (1% NaCl + surfactant (rapizol, manufactured by NOF Corporation) 200 mg / L) with ethanol at a ratio of 2: 1 was used.
- a voltage of 6.3 V was applied, the current value after 4 seconds was measured, and evaluation was performed as follows.
- ⁇ ... 0.005mA or less More than 0.005 mA and 0.05 mA or less, ⁇ ⁇ ⁇ ⁇ More than 0.05mA and 0.5mA or less, ⁇ ⁇ ⁇ ⁇ Over 0.5mA
- Paraffin wax was applied to both sides of the obtained polyester resin-coated metal plate at 50 mg / m 2 on each side. After punching into a disk (blank) having a diameter of 151 mm, drawing was performed so that the polybutylene terephthalate layer A became the outer surface of the can, and processed into a 1st cup. Subsequently, a B / M (Body Maker) was used to make a DI can (No. 7 can) with a reduction ratio of 45% at a speed of 200 cpm, and it was confirmed whether or not the outer surface of the can was shaved. The results were evaluated as follows. ⁇ ⁇ ⁇ ⁇ At the level where actual production can be performed without external shavings. ⁇ : The level of production of the actual machine is difficult due to the occurrence of external scraping.
- Cuts were made on the entire circumference of the obtained cup with a cutter at positions 25 mm and 50 mm above the bottom from the bottom.
- the cup was submerged in a container filled with water and subjected to a retort sterilization treatment at 125 ° C. for 45 minutes.
- the maximum peel length of the film at the cut was measured.
- the evaluation was performed as follows. ⁇ ⁇ ⁇ ⁇ Peel length is 5mm or less ⁇ ⁇ ⁇ ⁇ Peel length is more than 5mm and 10mm or less ⁇ ⁇ ⁇ ⁇ Peel length is more than 10mm and 15mm or less ⁇ ⁇ ⁇ Peel length is more than 15mm and 20mm or less ⁇ ⁇ : The peel length exceeds 20 mm
- Example 2 The operation was performed in the same manner as in Example 1 except that the surface temperature of the laminating roll was set to 150 ° C.
- FIG. 5 shows a chart of the obtained X-ray diffraction peak.
- Example 3 The procedure was performed in the same manner as in Example 1 except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1.
- Example 4 The procedure was performed in the same manner as in Example 1 except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1.
- Example 5 Example 1 Example 1 was repeated except that the thickness of the biaxially stretched polybutylene terephthalate film forming the polybutylene terephthalate layer A was 25 ⁇ m, the heating temperature of the metal plate before lamination was 275 ° C., and the surface temperature of the laminating roll was 150 ° C. Was performed in the same manner as described above.
- Example 6 The procedure was performed in the same manner as in Example 5, except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was returned were as shown in Table 1.
- Example 1 (Comparative Example 1) Example 1 was repeated except that the heating temperature of the metal plate before lamination was 235 ° C and the surface temperature of the laminating roll was 165 ° C.
- Example 2 The procedure was performed in the same manner as in Example 1 except that the laminating speed was 40 mpm, the heating temperature of the metal plate before laminating was 240 ° C., the surface temperature of the laminating roll was 150 ° C., and the time T during which the orientation return occurred was 4 seconds. .
- Example 3 The procedure was performed in the same manner as in Example 6, except that the laminating speed was 150 mpm, the heating temperature of the metal plate before laminating was 265 ° C., the surface temperature of the laminating roll was 80 ° C., and the time T during which the orientation return occurred was 1 second. .
- Example 7 On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, on the other surface of the metal plate, a biaxially stretched film of a homopolymer of polyethylene terephthalate and a thickness of 12 ⁇ m were laminated under the condition that oriented crystals remain.
- the heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 1.
- Example 8 On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, a biaxially stretched film of a polyethylene terephthalate / isophthalate resin in which isophthalic acid was copolymerized at 11 mol% and a thickness of 19 ⁇ m were laminated on the other surface of the metal plate under the condition that no oriented crystals remain.
- the heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 2.
- Example 9 On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, on the other surface of the metal plate, a biaxially stretched film made of a blend resin of polyethylene terephthalate and polybutylene terephthalate (blend ratio 4: 6) and a thickness of 18 ⁇ m were laminated under the condition that no oriented crystals remain.
- the heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 3.
- the polyester resin-coated metal sheet according to the present embodiment exhibited excellent results in all items of impact resistance, moldability, retort adhesion, and retort brushing resistance.
- the impact resistance evaluation, the moldability evaluation, the retort adhesion evaluation, and the retort brushing evaluation were evaluated using containers.
- the container lid has a lower degree of processing than the container. Therefore, if the value of the X-ray diffraction intensity ratio R, which is a feature of the present invention, is within the specified range, the container lid is also evaluated for impact resistance. It can be clearly seen that all of the evaluations of moldability, evaluation of retort adhesion, and evaluation of retort brushing give good results.
- occurrence of retort brushing can be suppressed in a container such as a beverage can or a food can or a container lid. Further, it is possible to provide a polyester resin-coated metal plate excellent in impact resistance, moldability, retort adhesion, and the like, and has extremely high industrial applicability.
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Rigid Containers With Two Or More Constituent Elements (AREA)
Abstract
[Problem] To provide a polyester-resin-coated metal sheet in a beverage can, a food can, or another such container and/or a container lid, the polyester-resin-coated metal sheet being exceptional in terms of impact resistance, moldability, retort adhesion, and other such properties while also making it possible to suppress the occurrence of retort blushing (formation of white spots). [Solution] A polyester-resin-coated metal sheet characterized by having a metal sheet 1 and a polybutylene terephthalate layer A laminated so as to be in contact with at least one side of the metal sheet 1, the ratio R of the X-ray diffraction intensity of a (100) surface and the X-ray diffraction intensity of a (1-11) surface of the polybutylene terephthalate layer A being within the range of 1.3-6.6. In the X-ray diffraction intensity of the (100) surface, the diffraction angle 2θ has a maximum value confirmed to be in the range of 23.0-24.0°. In the X-ray diffraction intensity of the (1-11) surface, the diffraction angle 2θ has a maximum value confirmed to be in the range of 25.0-26.0°. The ratio R of the X-ray diffraction intensities satisfies the relationship R = (diffraction intensity of (100) surface)/(diffraction intensity of (1-11) surface).
Description
本発明は、ポリエステル樹脂被覆金属板、ポリエステル樹脂被覆金属板の製造方法、そのポリエステル樹脂被覆金属板からなる容器及び容器蓋に関する。
The present invention relates to a polyester resin-coated metal plate, a method for producing a polyester resin-coated metal plate, a container made of the polyester resin-coated metal plate, and a container lid.
従来、飲料や食品用の金属缶等の容器の材料として、熱可塑性樹脂フィルムを金属板表面に積層した樹脂被覆金属板が知られている。前記熱可塑性樹脂フィルムとしては、ポリエステルフィルム等が使用されている。
Conventionally, a resin-coated metal plate in which a thermoplastic resin film is laminated on a metal plate surface is known as a material for containers such as metal cans for beverages and foods. As the thermoplastic resin film, a polyester film or the like is used.
上記のような飲料や食品用の金属缶等の容器は、内容物を充填した後に行われるレトルト殺菌処理に耐えられる必要がある。レトルト殺菌処理は、バッチ式や連続式等の複数の方式が存在するが、例えばバッチ式レトルト処理は、高温のスチーム中に金属缶等の容器を数分~数十分間曝露する工程を含む。また、連続式レトルト処理は、エンドレスチェーンコンベアにより殺菌室に搬送された金属缶等の容器を、高温スチーム中に数分~数十分間曝露する工程を含む。なお近年では、生産性の向上を目的として、バッチ式に比して比較的新しい方式である連続式の製造ラインが増加している。
容器 Containers such as metal cans for beverages and foods as described above need to be able to withstand the retort sterilization performed after filling the contents. There are a plurality of retort sterilization processes such as a batch process and a continuous process. For example, the batch retort process includes a step of exposing a container such as a metal can to high-temperature steam for several minutes to several tens of minutes. . Further, the continuous retort treatment includes a step of exposing a container such as a metal can conveyed to a sterilization chamber by an endless chain conveyor into high-temperature steam for several minutes to tens of minutes. In recent years, continuous production lines, which are relatively new systems compared to the batch system, have been increasing for the purpose of improving productivity.
この新しい方式である連続式の製造ラインでは、充填後の容器を搬送しながら高温の熱湯に潜らせるなど、加熱昇温が非常に速いため、従来想定されていた以上に金属板の表面に積層された熱可塑性樹脂フィルムにとっては過酷な環境となっている。このような連続式の製造ラインの様な極めて昇温速度の速い、過酷なレトルト殺菌処理の環境を経ても、金属板からのフィルムのデラミネーション等が起こらない特性を有する熱可塑性樹脂フィルム被覆金属板が強く求められている。
In this new type of continuous production line, heating and heating are extremely fast, such as dipping the filled containers into high-temperature hot water while transporting them, so that the containers are stacked on the surface of the metal plate more than previously assumed. This is a severe environment for the thermoplastic resin film. A thermoplastic resin film-coated metal that has the property that delamination of a film from a metal plate does not occur even under a severe retort sterilization environment such as a continuous production line with a very high temperature rise rate. Boards are in great demand.
また、上記のようなレトルト殺菌処理時に、金属缶等の容器の外面側において、3ピース缶の天地蓋又は2ピース缶の缶底に発生し得るレトルトブラッシング(白斑)の問題が、従来検討されてきた。レトルトブラッシング(白斑)とは、上記レトルト殺菌処理を経た樹脂層が部分的に白くなり、外観を損ねる現象である。
In addition, during the retort sterilization treatment as described above, the problem of retort brushing (white spots) that may occur on the top lid of a three-piece can or the bottom of a two-piece can on the outer surface side of a container such as a metal can has been studied. Have been. The retort brushing (white spots) is a phenomenon in which the resin layer that has undergone the above-described retort sterilization treatment becomes partially white and impairs the appearance.
このようなレトルトブラッシング(白斑)の発生原因としてはいくつか考えられており、レトルト殺菌処理時において、缶蓋又は缶底に水滴が付着する部分とそうではない部分とが生じ、該水滴付着部分のフィルムがより速く結晶化するため、他の部分との比較で白く見えるものと推定されている。
There are several possible causes of the occurrence of such retort brushing (white spots). During the retort sterilization treatment, a portion where water droplets adhere to the can lid or the bottom of the can and a portion where water droplets do not adhere are formed. It is estimated that the film crystallizes faster and therefore looks whiter than other parts.
あるいは、缶蓋又は缶底に付着した水滴が熱可塑性樹脂フィルムを透過し、金属板と樹脂フィルムとの間で気泡となるためとも推定されている。また、レトルト殺菌処理の際、フィルム中に含水された水分が、その後の急激な昇温により気化温度に達するとフィルム内部で発泡するため、その部分が白く見えると推定されている。
いずれの場合もレトルト釜の昇温速度への依存が大きく、特に連続式の製造ラインの様に昇温速度が特に速いレトルト釜に適用できる熱可塑性樹脂被覆金属容器の開発が求められている。 Alternatively, it is also presumed that water droplets adhering to the can lid or the bottom of the can pass through the thermoplastic resin film and become bubbles between the metal plate and the resin film. In addition, during the retort sterilization treatment, it is presumed that the water contained in the film foams inside the film when it reaches the vaporization temperature due to a sudden rise in temperature, so that the portion looks white.
In any case, there is a great dependence on the heating rate of the retort pot, and there is a need for the development of a thermoplastic resin-coated metal container that can be applied to a retort pot with a particularly high heating rate, such as a continuous production line.
いずれの場合もレトルト釜の昇温速度への依存が大きく、特に連続式の製造ラインの様に昇温速度が特に速いレトルト釜に適用できる熱可塑性樹脂被覆金属容器の開発が求められている。 Alternatively, it is also presumed that water droplets adhering to the can lid or the bottom of the can pass through the thermoplastic resin film and become bubbles between the metal plate and the resin film. In addition, during the retort sterilization treatment, it is presumed that the water contained in the film foams inside the film when it reaches the vaporization temperature due to a sudden rise in temperature, so that the portion looks white.
In any case, there is a great dependence on the heating rate of the retort pot, and there is a need for the development of a thermoplastic resin-coated metal container that can be applied to a retort pot with a particularly high heating rate, such as a continuous production line.
このようなレトルトブラッシング(白斑)の問題を改善するために、熱可塑性樹脂フィルムとして、ポリエチレンテレフタレート(PET)にポリブチレンテレフタレート(PBT)をブレンドした樹脂を使用する方法が提案されている。PBTは結晶化速度が速いため、レトルト殺菌処理開始からの短時間でフィルムが結晶化することで水蒸気の透過を抑制し、レトルトブラッシング(白斑)の発生を抑制することが可能であるが、連続式の製造ラインの様にレトルト釜の昇温速度が非常に速い用途への適用はできていない。
方法 In order to improve such a problem of retort brushing (white spots), a method of using a resin in which polyethylene terephthalate (PET) is blended with polybutylene terephthalate (PBT) has been proposed as a thermoplastic resin film. Since PBT has a high crystallization rate, the film is crystallized in a short time from the start of the retort sterilization treatment, thereby suppressing water vapor transmission and suppressing the occurrence of retort brushing (white spots). It cannot be applied to applications in which the temperature of the retort kettle is extremely high, as in the production line of the formula.
一方で、より結晶化速度の速いポリブチレンテレフタレート(PBT)のホモポリマーであれば、その結晶化速度の速さによりレトルトブラッシング(白斑)への耐性をさらに向上させる方法として有効と考えられてきた。
On the other hand, a homopolymer of polybutylene terephthalate (PBT) having a higher crystallization rate has been considered to be effective as a method for further improving the resistance to retort brushing (white spots) due to the higher crystallization rate. .
例えば、特許文献1には、未配向のポリブチレンテレフタレート(PBT)のホモポリマーを鋼鈑上に被覆してなる容器用樹脂被覆鋼鈑が開示されている。
For example, Patent Literature 1 discloses a resin-coated steel sheet for a container in which a non-oriented polybutylene terephthalate (PBT) homopolymer is coated on a steel sheet.
また特許文献2には、飲料缶や食缶などの材料として用いられる缶用ラミネート金属板として、金属板面に接して、例えば二軸延伸ポリブチレンテレフタレートフィルムを積層したラミネート金属板が開示されている。
Patent Document 2 discloses a laminated metal plate in which a biaxially stretched polybutylene terephthalate film is laminated, for example, as a laminated metal plate for a can used as a material for a beverage can or a food can, in contact with the surface of the metal plate. I have.
特許文献1に開示される技術においては、特定のポリエステルフィルムを未配向状態とすることで、塗装焼付け工程や溶接工程におけるフィルムの熱脆化及び熱収縮の改善を目的としたものであるが、その容器の用途にはレトルト殺菌処理を前提としておらず、レトルト密着性が要求される場面を想定してその性能を確認するものではない。
The technique disclosed in Patent Document 1 aims at improving thermal embrittlement and thermal shrinkage of a film in a coating baking process and a welding process by setting a specific polyester film in an unoriented state. The use of the container is not premised on the retort sterilization treatment, and its performance is not confirmed on the assumption that retort adhesion is required.
一方で、特許文献2に開示するような延伸ポリブチレンテレフタレートフィルムは、延伸によりフィルム強度が大きく、また寸法安定性が良いのでフィルムの巻き形状が崩れ難いというメリットは存在する。すなわち、金属板へ積層する際のフィルム破断やフィルム皺発生等のリスクが低減するため、生産性の観点からは、延伸フィルムを使用することが好ましいとも言える。しかしながら、延伸ポリブチレンテレフタレートフィルムは延伸ポリエチレンテレフタレートフィルムよりも結晶性が高く、延伸による配向結晶によりフィルム内部に大きな残留応力を有しているため、樹脂被覆金属板を容器又は蓋に加工した場合、レトルト殺菌処理時にフィルムが剥離しやすいといった課題があった。
On the other hand, a stretched polybutylene terephthalate film as disclosed in Patent Literature 2 has the advantage that the film strength is large by stretching and the dimensional stability is good, so that the wound shape of the film is not easily collapsed. That is, it is preferable to use a stretched film from the viewpoint of productivity, since the risk of film breakage or film wrinkling when laminating on a metal plate is reduced. However, since the stretched polybutylene terephthalate film has higher crystallinity than the stretched polyethylene terephthalate film and has a large residual stress inside the film due to the oriented crystal by stretching, when the resin-coated metal plate is processed into a container or a lid, There was a problem that the film was easily peeled off during the retort sterilization treatment.
上記のような種々の問題に鑑みて本発明者らは、連続レトルト方式の様な非常に昇温速度の速いレトルト条件下におけるレトルトブラッシング(白斑)の問題を解決すると同時に、耐衝撃性、容器や容器蓋としての成形性、レトルト殺菌処理時におけるフィルムの密着性(レトルト密着性)を解決すべく、鋭意検討した。
In view of the various problems as described above, the present inventors have solved the problem of retort brushing (white spots) under retort conditions with a very high heating rate, such as a continuous retort method, and at the same time, have improved the impact resistance and the container. In order to solve the moldability of the film and the container lid, and the adhesiveness of the film during the retort sterilization treatment (retort adhesiveness), intensive studies were made.
その結果、ポリブチレンテレフタレートフィルムを積層したポリエステル樹脂被覆金属板において、フィルムの配向結晶を特定の状態に制御することにより、上記課題が同時に解決することを見出し、本発明に想到したものである。
As a result, it has been found that the above problems can be solved at the same time by controlling the oriented crystal of the film to a specific state in a polyester resin-coated metal plate on which a polybutylene terephthalate film is laminated, and arrived at the present invention.
本発明は、以下の特徴を有する。
(1)本発明のポリエステル樹脂被覆金属板は、金属板と、前記金属板の少なくとも片面に接するように積層されたポリブチレンテレフタレート層と、を有し、前記ポリブチレンテレフタレート層における(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内であることを特徴とする。(ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。)
(2)上記(1)に記載のポリエステル樹脂被覆金属板において、前記ポリブチレンテレフタレート層は、前記金属板の片面に積層されており、前記金属板の他方の面には前記ポリブチレンテレフタレート層とは異なるポリエステル樹脂層が積層されていることが好ましい。
(3)上記(2)に記載のポリエステル樹脂被覆金属板において、前記異なるポリエステル樹脂層は、ポリエチレンテレフタレート樹脂層、イソフタル酸が共重合されたポリエチレンテレフタレート樹脂層、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がブレンドされた樹脂層、および、イソフタル酸が共重合された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とがブレンドされた樹脂層の中から選択されるいずれかであることが好ましい。
(4)上記(2)又は(3)に記載のポリエステル樹脂被覆金属板において、前記異なるポリエステル樹脂層は、未配向の状態でラミネートされていることが好ましい。
(5)上記(1)~(4)のいずれかに記載のポリエステル樹脂被覆金属板において、前記X線回折強度比Rが、1.3以上3.0以下の範囲内であることが好ましい。
(6)上記(5)に記載のポリエステル樹脂被覆金属板において、前記X線回折強度比Rが、1.3以上2.7以下の範囲内であることが更に好ましい。
(7)本発明の容器は、上記した(1)~(6)のいずれかに記載のポリエステル樹脂被覆金属板を用いて成形されたことを特徴とする。
(8)本発明の容器蓋は、上記した(1)~(6)のいずれかに記載のポリエステル樹脂被覆金属板を用いて成形されたことを特徴とする。
(9)本発明のポリエステル樹脂被覆金属板の製造方法は、金属板の少なくとも片面に対し、積層後のポリブチレンテレフタレート層における(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内となるようにラミネートロールを用いて二軸延伸ポリブチレンテレフタレートフィルムを積層するポリエステル樹脂被覆金属板の製造方法であって、前記金属板の板温を240℃~300℃の範囲内とし、前記ラミネートロールの表面温度を30℃~180℃の範囲内としつつ、かつ、ラミネート前の金属板の板温とラミネートロールの表面温度との温度差を80℃以上確保した条件にて前記二軸延伸ポリブチレンテレフタレートフィルムを前記金属板に積層する積層工程と、前記積層工程の後で、前記積層工程により溶解した前記二軸延伸ポリブチレンテレフタレートフィルムの配向結晶が復帰する配向復帰工程と、前記配向復帰工程の後で、前記二軸延伸ポリブチレンテレフタレートフィルムが積層された金属板を急冷する急冷工程と、を含むことを特徴とする。(ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。) The present invention has the following features.
(1) A polyester resin-coated metal plate of the present invention has a metal plate and a polybutylene terephthalate layer laminated so as to be in contact with at least one surface of the metal plate, and the (100) plane in the polybutylene terephthalate layer Wherein the ratio R of the X-ray diffraction intensity to the X-ray diffraction intensity of the (1-11) plane is in the range of 1.3 or more and 6.6 or less. (However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.)
(2) In the polyester resin-coated metal plate according to the above (1), the polybutylene terephthalate layer is laminated on one surface of the metal plate, and the polybutylene terephthalate layer is formed on the other surface of the metal plate. Preferably, different polyester resin layers are laminated.
(3) In the polyester resin-coated metal sheet according to (2), the different polyester resin layer is a polyethylene terephthalate resin layer, a polyethylene terephthalate resin layer in which isophthalic acid is copolymerized, or a blend of polyethylene terephthalate and polybutylene terephthalate. Or a resin layer in which polyethylene terephthalate copolymerized with isophthalic acid and polybutylene terephthalate are blended.
(4) In the polyester resin-coated metal plate according to the above (2) or (3), it is preferable that the different polyester resin layers are laminated in a non-oriented state.
(5) In the polyester resin-coated metal sheet according to any one of the above (1) to (4), it is preferable that the X-ray diffraction intensity ratio R is in a range of 1.3 or more and 3.0 or less.
(6) In the polyester resin-coated metal sheet according to the above (5), it is more preferable that the X-ray diffraction intensity ratio R is in a range of 1.3 or more and 2.7 or less.
(7) A container of the present invention is formed by using the polyester resin-coated metal plate according to any one of the above (1) to (6).
(8) A container lid according to the present invention is formed by using the polyester resin-coated metal plate according to any one of the above (1) to (6).
(9) The method for producing a polyester resin-coated metal plate according to the present invention is characterized in that the X-ray diffraction intensity of the (100) plane and the X-ray A method for producing a polyester resin-coated metal plate, comprising laminating a biaxially stretched polybutylene terephthalate film using a laminating roll so that a line diffraction intensity ratio R falls within a range of 1.3 or more and 6.6 or less. The plate temperature of the plate is set in the range of 240 ° C. to 300 ° C., and the surface temperature of the laminating roll is set in the range of 30 ° C. to 180 ° C. A laminating step of laminating the biaxially stretched polybutylene terephthalate film on the metal plate under the condition that the temperature difference of 80 ° C. or more is secured, and after the laminating step, An orientation return step in which the oriented crystals of the biaxially oriented polybutylene terephthalate film dissolved in the laminating step are restored, and after the orientation return step, the metal plate on which the biaxially oriented polybutylene terephthalate film is laminated is quenched. And a quenching step. (However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.)
(1)本発明のポリエステル樹脂被覆金属板は、金属板と、前記金属板の少なくとも片面に接するように積層されたポリブチレンテレフタレート層と、を有し、前記ポリブチレンテレフタレート層における(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内であることを特徴とする。(ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。)
(2)上記(1)に記載のポリエステル樹脂被覆金属板において、前記ポリブチレンテレフタレート層は、前記金属板の片面に積層されており、前記金属板の他方の面には前記ポリブチレンテレフタレート層とは異なるポリエステル樹脂層が積層されていることが好ましい。
(3)上記(2)に記載のポリエステル樹脂被覆金属板において、前記異なるポリエステル樹脂層は、ポリエチレンテレフタレート樹脂層、イソフタル酸が共重合されたポリエチレンテレフタレート樹脂層、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がブレンドされた樹脂層、および、イソフタル酸が共重合された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とがブレンドされた樹脂層の中から選択されるいずれかであることが好ましい。
(4)上記(2)又は(3)に記載のポリエステル樹脂被覆金属板において、前記異なるポリエステル樹脂層は、未配向の状態でラミネートされていることが好ましい。
(5)上記(1)~(4)のいずれかに記載のポリエステル樹脂被覆金属板において、前記X線回折強度比Rが、1.3以上3.0以下の範囲内であることが好ましい。
(6)上記(5)に記載のポリエステル樹脂被覆金属板において、前記X線回折強度比Rが、1.3以上2.7以下の範囲内であることが更に好ましい。
(7)本発明の容器は、上記した(1)~(6)のいずれかに記載のポリエステル樹脂被覆金属板を用いて成形されたことを特徴とする。
(8)本発明の容器蓋は、上記した(1)~(6)のいずれかに記載のポリエステル樹脂被覆金属板を用いて成形されたことを特徴とする。
(9)本発明のポリエステル樹脂被覆金属板の製造方法は、金属板の少なくとも片面に対し、積層後のポリブチレンテレフタレート層における(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内となるようにラミネートロールを用いて二軸延伸ポリブチレンテレフタレートフィルムを積層するポリエステル樹脂被覆金属板の製造方法であって、前記金属板の板温を240℃~300℃の範囲内とし、前記ラミネートロールの表面温度を30℃~180℃の範囲内としつつ、かつ、ラミネート前の金属板の板温とラミネートロールの表面温度との温度差を80℃以上確保した条件にて前記二軸延伸ポリブチレンテレフタレートフィルムを前記金属板に積層する積層工程と、前記積層工程の後で、前記積層工程により溶解した前記二軸延伸ポリブチレンテレフタレートフィルムの配向結晶が復帰する配向復帰工程と、前記配向復帰工程の後で、前記二軸延伸ポリブチレンテレフタレートフィルムが積層された金属板を急冷する急冷工程と、を含むことを特徴とする。(ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。) The present invention has the following features.
(1) A polyester resin-coated metal plate of the present invention has a metal plate and a polybutylene terephthalate layer laminated so as to be in contact with at least one surface of the metal plate, and the (100) plane in the polybutylene terephthalate layer Wherein the ratio R of the X-ray diffraction intensity to the X-ray diffraction intensity of the (1-11) plane is in the range of 1.3 or more and 6.6 or less. (However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.)
(2) In the polyester resin-coated metal plate according to the above (1), the polybutylene terephthalate layer is laminated on one surface of the metal plate, and the polybutylene terephthalate layer is formed on the other surface of the metal plate. Preferably, different polyester resin layers are laminated.
(3) In the polyester resin-coated metal sheet according to (2), the different polyester resin layer is a polyethylene terephthalate resin layer, a polyethylene terephthalate resin layer in which isophthalic acid is copolymerized, or a blend of polyethylene terephthalate and polybutylene terephthalate. Or a resin layer in which polyethylene terephthalate copolymerized with isophthalic acid and polybutylene terephthalate are blended.
(4) In the polyester resin-coated metal plate according to the above (2) or (3), it is preferable that the different polyester resin layers are laminated in a non-oriented state.
(5) In the polyester resin-coated metal sheet according to any one of the above (1) to (4), it is preferable that the X-ray diffraction intensity ratio R is in a range of 1.3 or more and 3.0 or less.
(6) In the polyester resin-coated metal sheet according to the above (5), it is more preferable that the X-ray diffraction intensity ratio R is in a range of 1.3 or more and 2.7 or less.
(7) A container of the present invention is formed by using the polyester resin-coated metal plate according to any one of the above (1) to (6).
(8) A container lid according to the present invention is formed by using the polyester resin-coated metal plate according to any one of the above (1) to (6).
(9) The method for producing a polyester resin-coated metal plate according to the present invention is characterized in that the X-ray diffraction intensity of the (100) plane and the X-ray A method for producing a polyester resin-coated metal plate, comprising laminating a biaxially stretched polybutylene terephthalate film using a laminating roll so that a line diffraction intensity ratio R falls within a range of 1.3 or more and 6.6 or less. The plate temperature of the plate is set in the range of 240 ° C. to 300 ° C., and the surface temperature of the laminating roll is set in the range of 30 ° C. to 180 ° C. A laminating step of laminating the biaxially stretched polybutylene terephthalate film on the metal plate under the condition that the temperature difference of 80 ° C. or more is secured, and after the laminating step, An orientation return step in which the oriented crystals of the biaxially oriented polybutylene terephthalate film dissolved in the laminating step are restored, and after the orientation return step, the metal plate on which the biaxially oriented polybutylene terephthalate film is laminated is quenched. And a quenching step. (However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.)
本発明によれば、レトルト殺菌処理時におけるレトルトブラッシング(白斑)の問題を解決すると同時に(レトルトブラッシング耐性)、絞り加工やしごき加工等の厳しい加工を施した後における耐衝撃性、製缶時の絞り加工やしごき加工等の厳しい加工に耐えられる成形性、レトルト殺菌処理時におけるフィルムと金属板との密着性(レトルト密着性)、等に優れたポリエステル樹脂被覆金属板を提供することができる。
また本発明によれば、ポリエステル樹脂被覆金属板の製造方法、ポリエステル樹脂被覆金属板からなる容器及び容器蓋を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while resolving the problem of retort brushing (white spots) at the time of retort sterilization treatment (resistance to retort brushing), impact resistance after performing severe processing such as drawing and ironing, and can production. It is possible to provide a polyester resin-coated metal plate excellent in moldability that can withstand severe processing such as drawing and ironing, and adhesion between the film and the metal plate during retort sterilization (retort adhesion).
Further, according to the present invention, it is possible to provide a method for producing a polyester resin-coated metal plate, a container made of the polyester resin-coated metal plate, and a container lid.
また本発明によれば、ポリエステル樹脂被覆金属板の製造方法、ポリエステル樹脂被覆金属板からなる容器及び容器蓋を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while resolving the problem of retort brushing (white spots) at the time of retort sterilization treatment (resistance to retort brushing), impact resistance after performing severe processing such as drawing and ironing, and can production. It is possible to provide a polyester resin-coated metal plate excellent in moldability that can withstand severe processing such as drawing and ironing, and adhesion between the film and the metal plate during retort sterilization (retort adhesion).
Further, according to the present invention, it is possible to provide a method for producing a polyester resin-coated metal plate, a container made of the polyester resin-coated metal plate, and a container lid.
以下、本発明を以下の実施形態により詳細に説明する。なお、本発明は以下の実施形態に限定されるものではない。
Hereinafter, the present invention will be described in detail by the following embodiments. Note that the present invention is not limited to the following embodiments.
[ポリエステル樹脂被覆金属板]
図1に示すように、本実施形態におけるポリエステル樹脂被覆金属板は、金属板1と、前記金属板1の少なくとも片面に接するように積層(ラミネート)されたポリブチレンテレフタレート層Aとを含む。
なお、前記ポリブチレンテレフタレート層Aは、前記金属板1が容器や容器蓋に成形された場合に、外面となる側に設けられることが好ましい。 [Polyester resin coated metal plate]
As shown in FIG. 1, the polyester resin-coated metal plate in the present embodiment includes ametal plate 1 and a polybutylene terephthalate layer A laminated (laminated) so as to be in contact with at least one surface of the metal plate 1.
The polybutylene terephthalate layer A is preferably provided on the outer side when themetal plate 1 is formed into a container or a container lid.
図1に示すように、本実施形態におけるポリエステル樹脂被覆金属板は、金属板1と、前記金属板1の少なくとも片面に接するように積層(ラミネート)されたポリブチレンテレフタレート層Aとを含む。
なお、前記ポリブチレンテレフタレート層Aは、前記金属板1が容器や容器蓋に成形された場合に、外面となる側に設けられることが好ましい。 [Polyester resin coated metal plate]
As shown in FIG. 1, the polyester resin-coated metal plate in the present embodiment includes a
The polybutylene terephthalate layer A is preferably provided on the outer side when the
<金属板1>
前記金属板1としては、通常の金属缶等の容器や容器蓋に使用される公知の金属板を使用することが可能であり、特に制限されるものではない。例えば好ましく使用される金属板として、表面処理鋼板や、アルミニウム板及びアルミニウム合金板等の軽金属板を使用することができる。 <Metal plate 1>
As themetal plate 1, a known metal plate used for a container such as a normal metal can or a container lid can be used, and is not particularly limited. For example, as a metal plate that is preferably used, a surface-treated steel plate or a light metal plate such as an aluminum plate and an aluminum alloy plate can be used.
前記金属板1としては、通常の金属缶等の容器や容器蓋に使用される公知の金属板を使用することが可能であり、特に制限されるものではない。例えば好ましく使用される金属板として、表面処理鋼板や、アルミニウム板及びアルミニウム合金板等の軽金属板を使用することができる。 <
As the
表面処理鋼板としては、アルミキルド鋼や低炭素鋼等が使用できる。例えば、冷延鋼板を焼鈍した後に二次冷間圧延し、錫めっき、ニッケルめっき、亜鉛めっき、電解クロム酸処理、クロム酸処理、アルミやジルコニウムを用いたノンクロム処理などの、一種または二種以上を行ったものを用いることができる。
、 Aluminum killed steel, low carbon steel, etc. can be used as the surface-treated steel sheet. For example, after cold-rolled steel sheet is subjected to secondary cold rolling, tin plating, nickel plating, zinc plating, electrolytic chromic acid treatment, chromic acid treatment, non-chromium treatment using aluminum or zirconium, one or more types Can be used.
軽金属板としては、アルミニウム板およびアルミニウム合金板が使用される。アルミニウム合金板としては、金属缶体用としては、例えば、JIS A3000系(Al-Mn系)を使用することができる。また、缶蓋用としては、例えば、JIS A5000系(Al-Mg系)を使用することができる。
なお、金属板の厚み等は、使用目的に応じて適宜選択することができる。 As the light metal plate, an aluminum plate and an aluminum alloy plate are used. As the aluminum alloy plate, for metal cans, for example, JIS A3000 (Al-Mn) can be used. For the can lid, for example, JIS A5000-based (Al-Mg-based) can be used.
The thickness and the like of the metal plate can be appropriately selected according to the purpose of use.
なお、金属板の厚み等は、使用目的に応じて適宜選択することができる。 As the light metal plate, an aluminum plate and an aluminum alloy plate are used. As the aluminum alloy plate, for metal cans, for example, JIS A3000 (Al-Mn) can be used. For the can lid, for example, JIS A5000-based (Al-Mg-based) can be used.
The thickness and the like of the metal plate can be appropriately selected according to the purpose of use.
<ポリブチレンテレフタレート層A>
本実施形態において、上記金属板1の少なくとも片面にはポリブチレンテレフタレート層Aが設けられている。このポリブチレンテレフタレート層Aは、ポリブチレンテレフタレート(PBT)のホモポリマーからなることを特徴とする。すなわち、本実施形態のポリブチレンテレフタレート層Aは、ポリエチレンテレフタレート(PET)等とのブレンドフィルムではなく、また、イソフタレート等の共重合成分も含まない。 <Polybutylene terephthalate layer A>
In this embodiment, a polybutylene terephthalate layer A is provided on at least one surface of themetal plate 1. The polybutylene terephthalate layer A is characterized by being composed of a homopolymer of polybutylene terephthalate (PBT). That is, the polybutylene terephthalate layer A of the present embodiment is not a blend film with polyethylene terephthalate (PET) or the like, and does not include a copolymer component such as isophthalate.
本実施形態において、上記金属板1の少なくとも片面にはポリブチレンテレフタレート層Aが設けられている。このポリブチレンテレフタレート層Aは、ポリブチレンテレフタレート(PBT)のホモポリマーからなることを特徴とする。すなわち、本実施形態のポリブチレンテレフタレート層Aは、ポリエチレンテレフタレート(PET)等とのブレンドフィルムではなく、また、イソフタレート等の共重合成分も含まない。 <Polybutylene terephthalate layer A>
In this embodiment, a polybutylene terephthalate layer A is provided on at least one surface of the
本実施形態におけるポリブチレンテレフタレート(PBT)のホモポリマーは、その融点(Tm)が215℃~225℃、固有粘度(IV値)が1.15~1.30dl/gの範囲であることが好ましい。なお、必要に応じて滑剤、アンチブロッキング剤、無機増量剤、酸化防止剤、紫外線吸収剤、帯電防止剤、難燃剤、可塑剤、着色剤、結晶化抑制剤、結晶化促進剤等の添加剤を加えてもよい。
またポリブチレンテレフタレートフィルムの製造方法としては、結晶化速度の速さから逐次二軸延伸法の適用は困難であり、同時二軸延伸法による製造が一般的である。同時二軸延伸法としては、チューブラー方式やテンター方式が挙げられるが、縦横の強度バランスが良い点でチューブラー方式が特に好ましい。延伸倍率はフィルムの強度物性、透明性、及び厚みの均一性を考慮して、MD、及びTDそれぞれ2.7~4.5倍の範囲であることが好ましい。 The homopolymer of polybutylene terephthalate (PBT) in the present embodiment preferably has a melting point (Tm) of 215 ° C. to 225 ° C. and an intrinsic viscosity (IV value) of 1.15 to 1.30 dl / g. . In addition, additives such as a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, and a crystallization accelerator, as necessary. May be added.
Further, as a method for producing a polybutylene terephthalate film, it is difficult to apply a sequential biaxial stretching method due to a high crystallization rate, and production by a simultaneous biaxial stretching method is general. Examples of the simultaneous biaxial stretching method include a tubular method and a tenter method, but the tubular method is particularly preferable in that the strength balance in the vertical and horizontal directions is good. The stretching ratio is preferably in the range of 2.7 to 4.5 times for each of MD and TD in consideration of the strength physical properties, transparency, and thickness uniformity of the film.
またポリブチレンテレフタレートフィルムの製造方法としては、結晶化速度の速さから逐次二軸延伸法の適用は困難であり、同時二軸延伸法による製造が一般的である。同時二軸延伸法としては、チューブラー方式やテンター方式が挙げられるが、縦横の強度バランスが良い点でチューブラー方式が特に好ましい。延伸倍率はフィルムの強度物性、透明性、及び厚みの均一性を考慮して、MD、及びTDそれぞれ2.7~4.5倍の範囲であることが好ましい。 The homopolymer of polybutylene terephthalate (PBT) in the present embodiment preferably has a melting point (Tm) of 215 ° C. to 225 ° C. and an intrinsic viscosity (IV value) of 1.15 to 1.30 dl / g. . In addition, additives such as a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, and a crystallization accelerator, as necessary. May be added.
Further, as a method for producing a polybutylene terephthalate film, it is difficult to apply a sequential biaxial stretching method due to a high crystallization rate, and production by a simultaneous biaxial stretching method is general. Examples of the simultaneous biaxial stretching method include a tubular method and a tenter method, but the tubular method is particularly preferable in that the strength balance in the vertical and horizontal directions is good. The stretching ratio is preferably in the range of 2.7 to 4.5 times for each of MD and TD in consideration of the strength physical properties, transparency, and thickness uniformity of the film.
<X線回折強度比>
本実施形態におけるポリブチレンテレフタレート層Aは、(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内であることを特徴とする。ここで、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値である。また、前記X線回折強度比Rは、「(100)面の回折強度/(1-11)面の回折強度」の値を表すものとする。
また、本明細書においては、表記の都合上、
を「(1-11)面」と記載するものとする。 <X-ray diffraction intensity ratio>
In the polybutylene terephthalate layer A in the present embodiment, the ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is in the range of 1.3 or more and 6.6 or less. Features. Here, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value observed when the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °. The X-ray diffraction intensity ratio R represents the value of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”.
In this specification, for convenience of notation,
Is described as “(1-11) plane”.
本実施形態におけるポリブチレンテレフタレート層Aは、(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内であることを特徴とする。ここで、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値である。また、前記X線回折強度比Rは、「(100)面の回折強度/(1-11)面の回折強度」の値を表すものとする。
また、本明細書においては、表記の都合上、
を「(1-11)面」と記載するものとする。 <X-ray diffraction intensity ratio>
In the polybutylene terephthalate layer A in the present embodiment, the ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is in the range of 1.3 or more and 6.6 or less. Features. Here, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value observed when the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °. The X-ray diffraction intensity ratio R represents the value of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”.
In this specification, for convenience of notation,
Is described as “(1-11) plane”.
一般的に、X線回折において回折角2θが23.0°~24.0°の範囲に確認されるピークは、PBTの配向結晶によりもたらされる強度であることが知られている。これは、PBTの分子鎖中のベンゼン環が(100)面に面配向することが理由である。
Generally, it is known that the peak at which the diffraction angle 2θ is found in the range of 23.0 ° to 24.0 ° in X-ray diffraction is the intensity caused by the oriented crystal of PBT. This is because the benzene ring in the molecular chain of PBT is plane-oriented to the (100) plane.
一方で、回折角2θが25.0°~26.0°の範囲に確認されるピークは、(1-11)面の回折強度である。(1-11)面は、フィルム表面の(100)面に対して45°に傾いた面である。
従って、(1-11)面由来のピークが観測されることは、PBT中におけるベンゼン環の一部が、フィルム表面に対して45°に傾いて配向していることを意味するものと考えられる。 On the other hand, the peak observed when the diffraction angle 2θ is in the range of 25.0 ° to 26.0 ° is the diffraction intensity of the (1-11) plane. The (1-11) plane is a plane inclined at 45 ° with respect to the (100) plane of the film surface.
Therefore, the observation of the peak derived from the (1-11) plane is considered to mean that a part of the benzene ring in the PBT is oriented at 45 ° to the film surface. .
従って、(1-11)面由来のピークが観測されることは、PBT中におけるベンゼン環の一部が、フィルム表面に対して45°に傾いて配向していることを意味するものと考えられる。 On the other hand, the peak observed when the diffraction angle 2θ is in the range of 25.0 ° to 26.0 ° is the diffraction intensity of the (1-11) plane. The (1-11) plane is a plane inclined at 45 ° with respect to the (100) plane of the film surface.
Therefore, the observation of the peak derived from the (1-11) plane is considered to mean that a part of the benzene ring in the PBT is oriented at 45 ° to the film surface. .
なお、上記(1-11)面由来のピークは、ポリエチレンテレフタレート(PET)のホモポリマー、ポリエチレンテレフタレートとイソフタレートの共重合フィルム(PET/I)、及びPETとPBTのブレンドフィルム、のいずれにおいても強く観測されるものではない。よって、(1-11)面由来のピークは、PBTホモポリマーにおける特有の現象と推測される。
The peak derived from the (1-11) plane is observed in any of a homopolymer of polyethylene terephthalate (PET), a copolymer film of polyethylene terephthalate and isophthalate (PET / I), and a blend film of PET and PBT. It is not strongly observed. Therefore, the peak derived from the (1-11) plane is presumed to be a peculiar phenomenon in the PBT homopolymer.
本実施形態において、(100)面のX線回折強度と(1-11)面のX線回折強度比Rを規定する意味は以下のとおりである。
上述したように、PBTのX線回折強度は、分子鎖中のベンゼン環の向きが特定の面に揃うことで強く現れることが知られている。 In the present embodiment, the meaning of defining the X-ray diffraction intensity ratio R of the (100) plane and the X-ray diffraction intensity of the (1-11) plane is as follows.
As described above, it is known that the X-ray diffraction intensity of PBT appears strongly when the orientation of the benzene ring in the molecular chain is aligned with a specific plane.
上述したように、PBTのX線回折強度は、分子鎖中のベンゼン環の向きが特定の面に揃うことで強く現れることが知られている。 In the present embodiment, the meaning of defining the X-ray diffraction intensity ratio R of the (100) plane and the X-ray diffraction intensity of the (1-11) plane is as follows.
As described above, it is known that the X-ray diffraction intensity of PBT appears strongly when the orientation of the benzene ring in the molecular chain is aligned with a specific plane.
延伸によりもたらされる配向結晶では、ベンゼン環がフィルム表面に平行に揃うため(100)面にX線回折強度が現れる。
配 向 In the oriented crystal obtained by stretching, the benzene rings are aligned parallel to the film surface, so that the X-ray diffraction intensity appears on the (100) plane.
一方で、例えば延伸フィルムを加熱した金属板に接触させてラミネートする際には、ラミネート時の熱により延伸フィルムが溶融することで、延伸による配向結晶が崩れる。その後、ラミネート直後からラミネート板を急冷するまでの間において、崩れた配向結晶が元の配向状態に戻ろうとする現象が発生する(以下、本発明ではこの現象に着目して、『配向復帰』とも称する)。この配向復帰は、上述したとおり、PBTの結晶化速度の速さに起因するものと考えられる。
On the other hand, for example, when the stretched film is brought into contact with a heated metal plate for lamination, the stretched film is melted by the heat during lamination, and the oriented crystals due to stretching are broken. Thereafter, during the period from immediately after lamination until the laminate plate is rapidly cooled, a phenomenon occurs in which the collapsed oriented crystal tends to return to the original orientation state (hereinafter, in the present invention, focusing on this phenomenon, it is also referred to as “orientation return”). Name). It is considered that this orientation return is caused by the crystallization speed of PBT as described above.
この配向復帰により、(1-11)面に新たなX線回折強度が現れることが知見として得られた。この(1-11)面におけるX線回折強度のピークは、PBTホモポリマーの二軸延伸フィルムには観測されないが、前記二軸延伸フィルムを特定のラミネート条件にて熱圧着したラミネート金属板においては観測されることが、本発明では確認されている。
知 見 It has been found that a new X-ray diffraction intensity appears on the (1-11) plane due to this orientation return. The peak of the X-ray diffraction intensity in the (1-11) plane is not observed in the biaxially stretched film of the PBT homopolymer, but in the laminated metal plate obtained by thermocompression-bonding the biaxially stretched film under specific laminating conditions. Observation has been confirmed in the present invention.
したがって本発明者らは、ポリエステル樹脂被覆金属板のポリブチレンテレフタレート層Aにおいて、上記配向結晶の量と配向復帰の量を厳密に管理することにより、耐衝撃性、成形性、レトルト密着性、の全てにおいて好ましい結果となることを見出した。そして、上記配向結晶の量と配向復帰の量を厳密に管理する方法として、(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内とすることに到達したのである。
Therefore, the present inventors, in the polybutylene terephthalate layer A of the polyester resin-coated metal plate, by strictly controlling the amount of the oriented crystal and the amount of the orientation return, impact resistance, moldability, retort adhesion, It has been found that favorable results are obtained in all cases. As a method of strictly controlling the amount of the oriented crystal and the amount of the orientation return, the ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is 1.3 or more. That is, the range of 6 or less was reached.
なお、上記では、二軸延伸PBTフィルムを金属板に熱接着する方法によりX線回折強度比Rの値を好ましい範囲内にする例を記載したが、本実施形態はこの例に制限されるものではない。
すなわち、熱接着以外の方法によっても、ラミネート後のPBTフィルムのX線回折強度比Rを規定の範囲内とすれば、本発明の要求する耐衝撃性、成形性、レトルト密着性、レトルトブラッシング耐性、のいずれにおいても好ましい特性を得ることが可能である。 In the above description, an example is described in which the value of the X-ray diffraction intensity ratio R is set in a preferable range by a method of thermally bonding a biaxially stretched PBT film to a metal plate, but the present embodiment is limited to this example. is not.
That is, if the X-ray diffraction intensity ratio R of the laminated PBT film is within the specified range by a method other than the thermal bonding, the impact resistance, moldability, retort adhesion, retort brushing resistance required by the present invention are required. , It is possible to obtain preferable characteristics.
すなわち、熱接着以外の方法によっても、ラミネート後のPBTフィルムのX線回折強度比Rを規定の範囲内とすれば、本発明の要求する耐衝撃性、成形性、レトルト密着性、レトルトブラッシング耐性、のいずれにおいても好ましい特性を得ることが可能である。 In the above description, an example is described in which the value of the X-ray diffraction intensity ratio R is set in a preferable range by a method of thermally bonding a biaxially stretched PBT film to a metal plate, but the present embodiment is limited to this example. is not.
That is, if the X-ray diffraction intensity ratio R of the laminated PBT film is within the specified range by a method other than the thermal bonding, the impact resistance, moldability, retort adhesion, retort brushing resistance required by the present invention are required. , It is possible to obtain preferable characteristics.
二軸延伸PBTフィルムの配向結晶をラミネートの際に発生する熱によって崩す場合、ラミネート後の(100)面のX線回折強度のピークがラミネート前のフィルム原反の(100)面のX線回折強度のピークの60%以下となる範囲で(1-11)面のX線回折強度のピークが現れることが確認できた。これは(100)面のX線回折強度が60%以下となる領域において、ラミネートの際に金属板と二軸延伸PBTフィルムの接触側に配向結晶が完全に溶解した「メルト層」と呼ばれる未配向の層が形成されるためと推測される。この「メルト層」は厚いほど密着性の向上に寄与することが知られているが、PBTの様に結晶化速度の速い樹脂の場合では、この「メルト層」が急冷されるまでの極短時間で配向復帰するため、(1-11)面にX線回折強度のピークが現れると推測される。
故に(1-11)面のX線回折強度のピークは配向結晶の指標である(100)面のX線回折強度のピーク変化と連動するパラメータであるといえる。さらに配向結晶を熱により崩して行くと、(1-11)面のX線回折強度のピークは緩やかに低下する一方で、配向結晶の指標である(100)面のX線回折強度はより大きな低下傾向を示す。本発明においては、この連動する二つのピーク強度の差が小さくなり、その強度比が上記の規定の範囲内となる場合において、成形性及びレトルト密着性を両立可能であることを見出した。
具体的には、(100)面のX線回折強度と(1-11)面のX線回折強度の比を6.6以下にする必要があることが確認できた。 When the oriented crystal of the biaxially stretched PBT film is broken by the heat generated during lamination, the peak of the X-ray diffraction intensity of the (100) plane after laminating is the X-ray diffraction of the (100) plane of the raw film before lamination. It was confirmed that an X-ray diffraction intensity peak of the (1-11) plane appeared within a range of 60% or less of the intensity peak. This is because in the region where the X-ray diffraction intensity on the (100) plane is 60% or less, the so-called “melt layer” in which the oriented crystals are completely dissolved on the contact side between the metal plate and the biaxially stretched PBT film during lamination. It is presumed that an oriented layer is formed. It is known that the thicker the “melt layer” is, the more it contributes to the improvement of adhesion. However, in the case of a resin having a high crystallization rate such as PBT, the extremely short time until the “melt layer” is rapidly cooled is obtained. It is estimated that the peak of the X-ray diffraction intensity appears on the (1-11) plane because the orientation is restored in time.
Therefore, it can be said that the peak of the X-ray diffraction intensity on the (1-11) plane is a parameter linked to the change in the peak of the X-ray diffraction intensity on the (100) plane, which is an index of the oriented crystal. When the oriented crystal is further broken down by heat, the peak of the X-ray diffraction intensity of the (1-11) plane gradually decreases, while the X-ray diffraction intensity of the (100) plane, which is an index of the oriented crystal, is larger. Shows a downward trend. In the present invention, it has been found that when the difference between the two peak intensities linked with each other is small and the intensity ratio is within the above-specified range, both the moldability and the retort adhesion can be achieved.
Specifically, it was confirmed that the ratio between the X-ray diffraction intensity of the (100) plane and the X-ray diffraction intensity of the (1-11) plane had to be 6.6 or less.
故に(1-11)面のX線回折強度のピークは配向結晶の指標である(100)面のX線回折強度のピーク変化と連動するパラメータであるといえる。さらに配向結晶を熱により崩して行くと、(1-11)面のX線回折強度のピークは緩やかに低下する一方で、配向結晶の指標である(100)面のX線回折強度はより大きな低下傾向を示す。本発明においては、この連動する二つのピーク強度の差が小さくなり、その強度比が上記の規定の範囲内となる場合において、成形性及びレトルト密着性を両立可能であることを見出した。
具体的には、(100)面のX線回折強度と(1-11)面のX線回折強度の比を6.6以下にする必要があることが確認できた。 When the oriented crystal of the biaxially stretched PBT film is broken by the heat generated during lamination, the peak of the X-ray diffraction intensity of the (100) plane after laminating is the X-ray diffraction of the (100) plane of the raw film before lamination. It was confirmed that an X-ray diffraction intensity peak of the (1-11) plane appeared within a range of 60% or less of the intensity peak. This is because in the region where the X-ray diffraction intensity on the (100) plane is 60% or less, the so-called “melt layer” in which the oriented crystals are completely dissolved on the contact side between the metal plate and the biaxially stretched PBT film during lamination. It is presumed that an oriented layer is formed. It is known that the thicker the “melt layer” is, the more it contributes to the improvement of adhesion. However, in the case of a resin having a high crystallization rate such as PBT, the extremely short time until the “melt layer” is rapidly cooled is obtained. It is estimated that the peak of the X-ray diffraction intensity appears on the (1-11) plane because the orientation is restored in time.
Therefore, it can be said that the peak of the X-ray diffraction intensity on the (1-11) plane is a parameter linked to the change in the peak of the X-ray diffraction intensity on the (100) plane, which is an index of the oriented crystal. When the oriented crystal is further broken down by heat, the peak of the X-ray diffraction intensity of the (1-11) plane gradually decreases, while the X-ray diffraction intensity of the (100) plane, which is an index of the oriented crystal, is larger. Shows a downward trend. In the present invention, it has been found that when the difference between the two peak intensities linked with each other is small and the intensity ratio is within the above-specified range, both the moldability and the retort adhesion can be achieved.
Specifically, it was confirmed that the ratio between the X-ray diffraction intensity of the (100) plane and the X-ray diffraction intensity of the (1-11) plane had to be 6.6 or less.
すなわち、ポリブチレンテレフタレート層A中に配向結晶が多く存在する場合、ポリブチレンテレフタレート層Aの伸びが低下するため、ポリエステル樹脂被覆金属板の成形性の低下の原因となる。また、レトルト殺菌処理の際にポリブチレンテレフタレート層Aの熱収縮応力が大きいため、金属板1からポリブチレンテレフタレート層Aが容易に剥離してしまうという問題が発生する(レトルト密着性の不足)。
That is, when a large number of oriented crystals exist in the polybutylene terephthalate layer A, the elongation of the polybutylene terephthalate layer A decreases, which causes a reduction in the moldability of the polyester resin-coated metal sheet. Further, since the heat shrinkage stress of the polybutylene terephthalate layer A is large at the time of the retort sterilization treatment, there is a problem that the polybutylene terephthalate layer A is easily separated from the metal plate 1 (insufficient retort adhesion).
そして延伸PBTフィルムにおいては、(100)面の他に(1-11)面にもX線回折強度が観測されることは上述のとおりである。この(1-11)面のX線回折強度は、フィルム中の配向結晶がラミネートの際の熱で完全に溶解した状態、いわゆる「メルト層」が金属板とフィルムの接触側に形成されたことを意味すると考えることができる。従って、(1-11)面にX線回折強度のピークが一定量確認できる状態は、密着性に対して有効に作用する「メルト層」が一定量形成された状態を表していると考えられる。
一方で、PBTは非常に結晶化速度の速い樹脂のため、ラミネート後に短時間で冷却を行わないと上記した配向復帰により、元の配向結晶状態に戻る割合が多くなり、結果として十分な密着性を確保できなくなる可能性がある。これらの推測から、(1-11)面のX線回折強度のピークは、密着性に有効に作用する「メルト層」が一定量形成されていることと、ラミネート後の配向復帰量が少量に抑制されていることを示す指標と成り得ると考えた。 As described above, in the stretched PBT film, X-ray diffraction intensity is observed not only on the (100) plane but also on the (1-11) plane. The X-ray diffraction intensity of the (1-11) plane was such that the oriented crystals in the film were completely dissolved by heat during lamination, that is, a so-called “melt layer” was formed on the contact side between the metal plate and the film. Can be considered. Therefore, the state where a certain amount of X-ray diffraction intensity peaks can be confirmed on the (1-11) plane is considered to indicate the state where a certain amount of “melt layer” that effectively acts on the adhesion is formed. .
On the other hand, since PBT is a resin with a very high crystallization rate, if the cooling is not performed in a short time after lamination, the above-mentioned orientation return increases the ratio of returning to the original oriented crystal state, resulting in sufficient adhesion. May not be able to be secured. From these estimations, the peak of the X-ray diffraction intensity of the (1-11) plane is that the "melt layer" which effectively acts on the adhesion is formed in a certain amount and the amount of the orientation return after lamination is small. We thought that it could be an index to show that it was suppressed.
一方で、PBTは非常に結晶化速度の速い樹脂のため、ラミネート後に短時間で冷却を行わないと上記した配向復帰により、元の配向結晶状態に戻る割合が多くなり、結果として十分な密着性を確保できなくなる可能性がある。これらの推測から、(1-11)面のX線回折強度のピークは、密着性に有効に作用する「メルト層」が一定量形成されていることと、ラミネート後の配向復帰量が少量に抑制されていることを示す指標と成り得ると考えた。 As described above, in the stretched PBT film, X-ray diffraction intensity is observed not only on the (100) plane but also on the (1-11) plane. The X-ray diffraction intensity of the (1-11) plane was such that the oriented crystals in the film were completely dissolved by heat during lamination, that is, a so-called “melt layer” was formed on the contact side between the metal plate and the film. Can be considered. Therefore, the state where a certain amount of X-ray diffraction intensity peaks can be confirmed on the (1-11) plane is considered to indicate the state where a certain amount of “melt layer” that effectively acts on the adhesion is formed. .
On the other hand, since PBT is a resin with a very high crystallization rate, if the cooling is not performed in a short time after lamination, the above-mentioned orientation return increases the ratio of returning to the original oriented crystal state, resulting in sufficient adhesion. May not be able to be secured. From these estimations, the peak of the X-ray diffraction intensity of the (1-11) plane is that the "melt layer" which effectively acts on the adhesion is formed in a certain amount and the amount of the orientation return after lamination is small. We thought that it could be an index to show that it was suppressed.
そして本発明者らは、(1-11)面におけるピーク強度に基づくパラメータを用いてフィルム中の配向結晶を制御することにより、PBT単体のフィルムにおいても要求される成形性及びレトルト密着性が達成できると考えた。
さらには、(100)面と(1-11)面の両方の結晶面におけるピーク強度の比により、成形性及びレトルト密着性の両方の特性をより好ましい次元で両立できると考えた。 By controlling the oriented crystals in the film using the parameters based on the peak intensity in the (1-11) plane, the present inventors have achieved the required formability and retort adhesion even in the PBT single film. I thought I could.
Furthermore, it was considered that both the properties of the moldability and the retort adhesion could be compatible with more preferable dimensions by the ratio of the peak intensities in both the (100) plane and the (1-11) plane.
さらには、(100)面と(1-11)面の両方の結晶面におけるピーク強度の比により、成形性及びレトルト密着性の両方の特性をより好ましい次元で両立できると考えた。 By controlling the oriented crystals in the film using the parameters based on the peak intensity in the (1-11) plane, the present inventors have achieved the required formability and retort adhesion even in the PBT single film. I thought I could.
Furthermore, it was considered that both the properties of the moldability and the retort adhesion could be compatible with more preferable dimensions by the ratio of the peak intensities in both the (100) plane and the (1-11) plane.
なお、(1-11)面のX線回折強度が(100)面のX線回折強度より大きくなることは現実的ではないので、X線回折強度比Rが1.3未満となることは現実的ではないといえる。
一方で、上記したX線回折強度比Rが6.6を超える場合は、(1-11)面の配向復帰の量に対して(100)面の配向結晶の量が多過ぎるため、絞り加工や絞りしごき加工等の厳しい加工を行う際や、レトルト殺菌処理時において、フィルムが金属板から剥離する可能性があり好ましくない。 Since it is not realistic that the X-ray diffraction intensity of the (1-11) plane is larger than the X-ray diffraction intensity of the (100) plane, it is not realistic that the X-ray diffraction intensity ratio R is less than 1.3. It is not a target.
On the other hand, when the above-mentioned X-ray diffraction intensity ratio R exceeds 6.6, the amount of the oriented crystal of the (100) plane is too large relative to the amount of the orientation return of the (1-11) plane. When performing severe processing such as drawing or drawing and ironing, or during retort sterilization, the film may peel off from the metal plate, which is not preferable.
一方で、上記したX線回折強度比Rが6.6を超える場合は、(1-11)面の配向復帰の量に対して(100)面の配向結晶の量が多過ぎるため、絞り加工や絞りしごき加工等の厳しい加工を行う際や、レトルト殺菌処理時において、フィルムが金属板から剥離する可能性があり好ましくない。 Since it is not realistic that the X-ray diffraction intensity of the (1-11) plane is larger than the X-ray diffraction intensity of the (100) plane, it is not realistic that the X-ray diffraction intensity ratio R is less than 1.3. It is not a target.
On the other hand, when the above-mentioned X-ray diffraction intensity ratio R exceeds 6.6, the amount of the oriented crystal of the (100) plane is too large relative to the amount of the orientation return of the (1-11) plane. When performing severe processing such as drawing or drawing and ironing, or during retort sterilization, the film may peel off from the metal plate, which is not preferable.
なお上記(100)面のX線回折強度と(1-11)面のX線回折強度比Rは、1.3以上3.0以下であることがより好ましく、1.3以上2.7以下であることがさらに好ましい。
The ratio R of the X-ray diffraction intensity of the (100) plane to the X-ray diffraction intensity of the (1-11) plane is more preferably 1.3 or more and 3.0 or less, and 1.3 or more and 2.7 or less. Is more preferable.
なお本実施形態において、ポリブチレンテレフタレート層AのX線回折におけるピーク強度の測定は、一般的な樹脂のX線回折測定方法により行うことができる。
例えば、ポリブチレンテレフタレート層Aを形成した金属板の樹脂被覆面を、X線回折装置を用い測定する。測定条件の例として、X線管球(ターゲット)としてCu(波長λ=0.1542nm)を使用して、管電圧40kV、管電流200mA程度で、回折ピークが分離できるように受光スリットを選択する。 In the present embodiment, the measurement of the peak intensity in the X-ray diffraction of the polybutylene terephthalate layer A can be performed by a general resin X-ray diffraction measurement method.
For example, the resin-coated surface of the metal plate on which the polybutylene terephthalate layer A is formed is measured using an X-ray diffractometer. As an example of the measurement conditions, Cu (wavelength λ = 0.1542 nm) is used as an X-ray tube (target), and a light receiving slit is selected so that a diffraction peak can be separated at a tube voltage of 40 kV and a tube current of about 200 mA. .
例えば、ポリブチレンテレフタレート層Aを形成した金属板の樹脂被覆面を、X線回折装置を用い測定する。測定条件の例として、X線管球(ターゲット)としてCu(波長λ=0.1542nm)を使用して、管電圧40kV、管電流200mA程度で、回折ピークが分離できるように受光スリットを選択する。 In the present embodiment, the measurement of the peak intensity in the X-ray diffraction of the polybutylene terephthalate layer A can be performed by a general resin X-ray diffraction measurement method.
For example, the resin-coated surface of the metal plate on which the polybutylene terephthalate layer A is formed is measured using an X-ray diffractometer. As an example of the measurement conditions, Cu (wavelength λ = 0.1542 nm) is used as an X-ray tube (target), and a light receiving slit is selected so that a diffraction peak can be separated at a tube voltage of 40 kV and a tube current of about 200 mA. .
回折角2θに対しX線の入射角と反射角がそれぞれθであり、かつ、入射X線と回折X線がフィルム面法線に対して対称となるように試料を取り付け、入射角θと反射角θが常に等しくなるように保ちながら、回折角2θを例えば10~30°の間で走査し、X線回折スペクトルを測定する。
なお、本実施形態においては、バックグラウンド補正は不要であり、得られたX線回折スペクトルのピーク高さはバックグラウンド補正無しで測定するものとする。 The sample is mounted so that the incident angle and the reflection angle of the X-ray are each θ with respect to the diffraction angle 2θ, and the incident X-ray and the diffraction X-ray are symmetric with respect to the normal to the film surface. The X-ray diffraction spectrum is measured by scanning the diffraction angle 2θ between, for example, 10 ° and 30 ° while keeping the angle θ always equal.
In the present embodiment, background correction is not required, and the peak height of the obtained X-ray diffraction spectrum is measured without background correction.
なお、本実施形態においては、バックグラウンド補正は不要であり、得られたX線回折スペクトルのピーク高さはバックグラウンド補正無しで測定するものとする。 The sample is mounted so that the incident angle and the reflection angle of the X-ray are each θ with respect to the diffraction angle 2θ, and the incident X-ray and the diffraction X-ray are symmetric with respect to the normal to the film surface. The X-ray diffraction spectrum is measured by scanning the diffraction angle 2θ between, for example, 10 ° and 30 ° while keeping the angle θ always equal.
In the present embodiment, background correction is not required, and the peak height of the obtained X-ray diffraction spectrum is measured without background correction.
なお、本実施形態において、ポリブチレンテレフタレート層Aは単層であることが好ましい。その理由としては以下の通りである。
すなわち上述したように、ポリブチレンテレフタレート(PBT)のホモポリマーは、その結晶化速度の速さによりレトルトブラッシング(白斑)の問題を改善するために有効である。仮にポリブチレンテレフタレート層Aを、PBTホモポリマー以外の樹脂との複層とした場合、PBTホモポリマー以外の樹脂層では結晶化速度が遅く不十分であり、十分な水蒸気バリア性を確保できない。その結果、PBTホモポリマー以外の樹脂層においてレトルトブラッシング(白斑)が発生してしまい、好ましくない。 In this embodiment, the polybutylene terephthalate layer A is preferably a single layer. The reasons are as follows.
That is, as described above, the homopolymer of polybutylene terephthalate (PBT) is effective for improving the problem of retort brushing (white spots) due to its high crystallization speed. If the polybutylene terephthalate layer A is formed as a multilayer with a resin other than the PBT homopolymer, the crystallization rate of the resin layer other than the PBT homopolymer is slow and insufficient, and a sufficient water vapor barrier property cannot be secured. As a result, retort brushing (white spots) occurs in the resin layer other than the PBT homopolymer, which is not preferable.
すなわち上述したように、ポリブチレンテレフタレート(PBT)のホモポリマーは、その結晶化速度の速さによりレトルトブラッシング(白斑)の問題を改善するために有効である。仮にポリブチレンテレフタレート層Aを、PBTホモポリマー以外の樹脂との複層とした場合、PBTホモポリマー以外の樹脂層では結晶化速度が遅く不十分であり、十分な水蒸気バリア性を確保できない。その結果、PBTホモポリマー以外の樹脂層においてレトルトブラッシング(白斑)が発生してしまい、好ましくない。 In this embodiment, the polybutylene terephthalate layer A is preferably a single layer. The reasons are as follows.
That is, as described above, the homopolymer of polybutylene terephthalate (PBT) is effective for improving the problem of retort brushing (white spots) due to its high crystallization speed. If the polybutylene terephthalate layer A is formed as a multilayer with a resin other than the PBT homopolymer, the crystallization rate of the resin layer other than the PBT homopolymer is slow and insufficient, and a sufficient water vapor barrier property cannot be secured. As a result, retort brushing (white spots) occurs in the resin layer other than the PBT homopolymer, which is not preferable.
金属板1上に形成されるポリブチレンテレフタレート層Aの厚みは、5~30μmであることが、成形性及び、レトルト殺菌処理時のレトルト密着性の観点からは好ましい。
The thickness of the polybutylene terephthalate layer A formed on the metal plate 1 is preferably 5 to 30 μm from the viewpoint of moldability and retort adhesion during retort sterilization.
ポリブチレンテレフタレート層Aの厚みが5μm未満である場合、成形後の金属露出部の割合が多くなり、レトルト殺菌後に錆が発生してしまう。
一方で、ポリブチレンテレフタレート層Aの厚みが30μmを超える場合は、フィルム内の残留応力が大き過ぎるため、レトルト密着性の確保が難しくなる点や、コストの観点から望ましくない。 When the thickness of the polybutylene terephthalate layer A is less than 5 μm, the ratio of the metal exposed portion after molding increases, and rust is generated after retort sterilization.
On the other hand, when the thickness of the polybutylene terephthalate layer A exceeds 30 μm, the residual stress in the film is too large, which makes it difficult to ensure retort adhesion and is undesirable from the viewpoint of cost.
一方で、ポリブチレンテレフタレート層Aの厚みが30μmを超える場合は、フィルム内の残留応力が大き過ぎるため、レトルト密着性の確保が難しくなる点や、コストの観点から望ましくない。 When the thickness of the polybutylene terephthalate layer A is less than 5 μm, the ratio of the metal exposed portion after molding increases, and rust is generated after retort sterilization.
On the other hand, when the thickness of the polybutylene terephthalate layer A exceeds 30 μm, the residual stress in the film is too large, which makes it difficult to ensure retort adhesion and is undesirable from the viewpoint of cost.
本実施形態におけるポリエステル樹脂被覆金属板は、上述したように、金属板1と、前記金属板1の少なくとも片面に接するように積層されたポリブチレンテレフタレート層Aとを含む。
ポ リ エ ス テ ル The polyester resin-coated metal plate in the present embodiment includes the metal plate 1 and the polybutylene terephthalate layer A laminated so as to be in contact with at least one surface of the metal plate 1 as described above.
なお、ポリブチレンテレフタレート層Aは、図2(a)に示すように金属板1の両面に積層されていても良い。また、図2(b)に示すように、金属板1の片面にはポリブチレンテレフタレート層Aが積層され、他方の面には、前記ポリブチレンテレフタレート層Aとは異なるポリエステル樹脂層Bが積層されていてもよい。
The polybutylene terephthalate layer A may be laminated on both sides of the metal plate 1 as shown in FIG. As shown in FIG. 2B, a polybutylene terephthalate layer A is laminated on one surface of the metal plate 1, and a polyester resin layer B different from the polybutylene terephthalate layer A is laminated on the other surface. May be.
なお、図面上の記載について、樹脂層と金属板の厚みは便宜的に模式化されて図示されているため、正確な厚み比とは異なるものである。
以下、上記のポリエステル樹脂層Bについて説明をする。 In the description on the drawings, the thickness of the resin layer and the thickness of the metal plate are schematically illustrated for the sake of convenience, and thus are different from the exact thickness ratio.
Hereinafter, the polyester resin layer B will be described.
以下、上記のポリエステル樹脂層Bについて説明をする。 In the description on the drawings, the thickness of the resin layer and the thickness of the metal plate are schematically illustrated for the sake of convenience, and thus are different from the exact thickness ratio.
Hereinafter, the polyester resin layer B will be described.
<ポリエステル樹脂層B>
ポリエステル樹脂層Bを構成するポリエステル樹脂としては、ポリエチレンテレフタレート樹脂、イソフタル酸が共重合されたポリエチレンテレフタレート/イソフタレート樹脂、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がブレンドされた樹脂、イソフタル酸が共重合されたポリエチレンテレフタレート/イソフタレートとポリブチレンテレフタレートとがブレンドされた樹脂、等を挙げることができる。しかしながら、これに限定されず、公知のポリエステル樹脂を適用することが可能である。 <Polyester resin layer B>
Examples of the polyester resin constituting the polyester resin layer B include polyethylene terephthalate resin, polyethylene terephthalate / isophthalate resin in which isophthalic acid is copolymerized, resin in which polyethylene terephthalate and polybutylene terephthalate are blended, and polyethylene in which isophthalic acid is copolymerized. Examples of the resin include a resin in which terephthalate / isophthalate and polybutylene terephthalate are blended. However, the invention is not limited thereto, and a known polyester resin can be applied.
ポリエステル樹脂層Bを構成するポリエステル樹脂としては、ポリエチレンテレフタレート樹脂、イソフタル酸が共重合されたポリエチレンテレフタレート/イソフタレート樹脂、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がブレンドされた樹脂、イソフタル酸が共重合されたポリエチレンテレフタレート/イソフタレートとポリブチレンテレフタレートとがブレンドされた樹脂、等を挙げることができる。しかしながら、これに限定されず、公知のポリエステル樹脂を適用することが可能である。 <Polyester resin layer B>
Examples of the polyester resin constituting the polyester resin layer B include polyethylene terephthalate resin, polyethylene terephthalate / isophthalate resin in which isophthalic acid is copolymerized, resin in which polyethylene terephthalate and polybutylene terephthalate are blended, and polyethylene in which isophthalic acid is copolymerized. Examples of the resin include a resin in which terephthalate / isophthalate and polybutylene terephthalate are blended. However, the invention is not limited thereto, and a known polyester resin can be applied.
ポリエステル樹脂層Bは、未配向の状態で積層されていることが、成形難易度が高い容器、例えばDI(Drawing&Ironing)缶などにおける成形性及びレトルト密着性確保の観点から好ましい。また、ポリエステル樹脂層Bは、単層であってもよいし、複層であってもよい。
It is preferable that the polyester resin layer B is laminated in an unoriented state from the viewpoint of ensuring moldability and retort adhesion in a container having high molding difficulty, for example, a DI (Drawing & Ironing) can. Further, the polyester resin layer B may be a single layer or a multilayer.
なお、上記したポリエステル樹脂層Bは、公知の添加剤、例えばアンチブロッキング剤、顔料、帯電防止剤、酸化防止剤、滑剤、等を、公知の処方によって配合することができる。
The above-mentioned polyester resin layer B can be blended with known additives, for example, an antiblocking agent, a pigment, an antistatic agent, an antioxidant, a lubricant and the like by a known formulation.
[ポリエステル樹脂被覆金属板の製造方法]
次に、本実施形態におけるポリエステル樹脂被覆金属板の製造方法について説明するが、本発明は以下の記載に制限されるものではない。
本実施形態のポリエステル樹脂被覆金属板は、金属板1の少なくとも片面にポリブチレンテレフタレート層Aを熱接着により形成することにより製造することができる。 [Method for producing polyester resin-coated metal plate]
Next, a method for producing a polyester resin-coated metal plate in the present embodiment will be described, but the present invention is not limited to the following description.
The polyester resin-coated metal plate of the present embodiment can be manufactured by forming a polybutylene terephthalate layer A on at least one surface of themetal plate 1 by thermal bonding.
次に、本実施形態におけるポリエステル樹脂被覆金属板の製造方法について説明するが、本発明は以下の記載に制限されるものではない。
本実施形態のポリエステル樹脂被覆金属板は、金属板1の少なくとも片面にポリブチレンテレフタレート層Aを熱接着により形成することにより製造することができる。 [Method for producing polyester resin-coated metal plate]
Next, a method for producing a polyester resin-coated metal plate in the present embodiment will be described, but the present invention is not limited to the following description.
The polyester resin-coated metal plate of the present embodiment can be manufactured by forming a polybutylene terephthalate layer A on at least one surface of the
本実施形態のポリエステル樹脂被覆金属板の製造方法は、金属板の少なくとも片面に対し、積層後のポリブチレンテレフタレート層Aにおける(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内となるようにラミネートロールを用いて二軸延伸ポリブチレンテレフタレートフィルムを積層するポリエステル樹脂被覆金属板の製造方法であって、具体的には以下の工程を有することを特徴とする。
(1)前記金属板の板温を240℃~300℃の範囲内とし、前記ラミネートロールの表面温度を30℃~180℃の範囲内としつつ、かつ、ラミネート前の金属板の板温とラミネートロールの表面温度との差を80℃以上確保した条件にて前記二軸延伸ポリブチレンテレフタレートフィルムを前記金属板に積層する積層工程;
(2)前記積層工程の後で、前記積層工程により溶解した前記二軸延伸ポリブチレンテレフタレートフィルムの配向結晶がラミネート直後の板温度の影響により復帰する配向復帰工程;
(3)前記配向復帰工程の後で、前記二軸延伸ポリブチレンテレフタレートフィルムが積層された金属板を急冷する急冷工程。 The method for producing a polyester resin-coated metal sheet according to the present embodiment is characterized in that the X-ray diffraction intensity of the (100) plane and the X-ray A method for producing a polyester resin-coated metal sheet, comprising laminating a biaxially stretched polybutylene terephthalate film using a laminating roll so that a diffraction intensity ratio R falls within a range of 1.3 or more and 6.6 or less. Is characterized by having the following steps.
(1) The temperature of the metal plate is set within a range of 240 ° C. to 300 ° C., the surface temperature of the laminating roll is set within a range of 30 ° C. to 180 ° C. A laminating step of laminating the biaxially stretched polybutylene terephthalate film on the metal plate under the condition that the difference from the surface temperature of the roll is maintained at 80 ° C. or more;
(2) after the laminating step, an orientation returning step in which the oriented crystals of the biaxially stretched polybutylene terephthalate film dissolved in the laminating step return due to the influence of the plate temperature immediately after lamination;
(3) A quenching step of quenching the metal plate on which the biaxially stretched polybutylene terephthalate film is laminated after the orientation return step.
(1)前記金属板の板温を240℃~300℃の範囲内とし、前記ラミネートロールの表面温度を30℃~180℃の範囲内としつつ、かつ、ラミネート前の金属板の板温とラミネートロールの表面温度との差を80℃以上確保した条件にて前記二軸延伸ポリブチレンテレフタレートフィルムを前記金属板に積層する積層工程;
(2)前記積層工程の後で、前記積層工程により溶解した前記二軸延伸ポリブチレンテレフタレートフィルムの配向結晶がラミネート直後の板温度の影響により復帰する配向復帰工程;
(3)前記配向復帰工程の後で、前記二軸延伸ポリブチレンテレフタレートフィルムが積層された金属板を急冷する急冷工程。 The method for producing a polyester resin-coated metal sheet according to the present embodiment is characterized in that the X-ray diffraction intensity of the (100) plane and the X-ray A method for producing a polyester resin-coated metal sheet, comprising laminating a biaxially stretched polybutylene terephthalate film using a laminating roll so that a diffraction intensity ratio R falls within a range of 1.3 or more and 6.6 or less. Is characterized by having the following steps.
(1) The temperature of the metal plate is set within a range of 240 ° C. to 300 ° C., the surface temperature of the laminating roll is set within a range of 30 ° C. to 180 ° C. A laminating step of laminating the biaxially stretched polybutylene terephthalate film on the metal plate under the condition that the difference from the surface temperature of the roll is maintained at 80 ° C. or more;
(2) after the laminating step, an orientation returning step in which the oriented crystals of the biaxially stretched polybutylene terephthalate film dissolved in the laminating step return due to the influence of the plate temperature immediately after lamination;
(3) A quenching step of quenching the metal plate on which the biaxially stretched polybutylene terephthalate film is laminated after the orientation return step.
ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。
以下、各工程について説明する。 However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is found in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is The diffraction angle 2θ is the maximum value observed in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity. is there.
Hereinafter, each step will be described.
以下、各工程について説明する。 However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is found in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is The diffraction angle 2θ is the maximum value observed in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity. is there.
Hereinafter, each step will be described.
まず、積層工程について説明する。
図3に示すように、金属板1を、図示しない加熱ロールにより240℃~300℃の温度に加熱する。そして加熱された金属板1を、ラミネートロール3A、3B間に供給する。
ここで、金属板1の加熱温度が240℃未満である場合、ポリブチレンテレフタレート層Aを形成した後に残存する二軸延伸PBTフィルムの(100)面のX線回折強度、すなわち配向結晶の量が多過ぎるため、X線回折強度比Rの値を好ましい範囲内とすることが困難であり、好ましくない。
一方で、金属板1の加熱温度が300℃を超える場合には、ポリブチレンテレフタレート層Aがラミネートの際、フィルム全体が溶融状態となってしまい、ラミネートロールに溶着する、もしくはラミネートロール表面の粗度が転写してしまうため好ましくない。 First, the laminating step will be described.
As shown in FIG. 3, themetal plate 1 is heated to a temperature of 240 ° C. to 300 ° C. by a heating roll (not shown). Then, the heated metal plate 1 is supplied between the laminating rolls 3A and 3B.
Here, when the heating temperature of themetal plate 1 is lower than 240 ° C., the X-ray diffraction intensity of the (100) plane of the biaxially stretched PBT film remaining after the formation of the polybutylene terephthalate layer A, that is, the amount of oriented crystals is reduced. Since it is too large, it is difficult to make the value of the X-ray diffraction intensity ratio R within a preferable range, which is not preferable.
On the other hand, when the heating temperature of themetal plate 1 exceeds 300 ° C., when the polybutylene terephthalate layer A is laminated, the whole film is in a molten state and is welded to the laminating roll or the surface of the laminating roll is rough. It is not preferable because the degree is transferred.
図3に示すように、金属板1を、図示しない加熱ロールにより240℃~300℃の温度に加熱する。そして加熱された金属板1を、ラミネートロール3A、3B間に供給する。
ここで、金属板1の加熱温度が240℃未満である場合、ポリブチレンテレフタレート層Aを形成した後に残存する二軸延伸PBTフィルムの(100)面のX線回折強度、すなわち配向結晶の量が多過ぎるため、X線回折強度比Rの値を好ましい範囲内とすることが困難であり、好ましくない。
一方で、金属板1の加熱温度が300℃を超える場合には、ポリブチレンテレフタレート層Aがラミネートの際、フィルム全体が溶融状態となってしまい、ラミネートロールに溶着する、もしくはラミネートロール表面の粗度が転写してしまうため好ましくない。 First, the laminating step will be described.
As shown in FIG. 3, the
Here, when the heating temperature of the
On the other hand, when the heating temperature of the
続いて、ポリブチレンテレフタレート層Aを形成するためのポリブチレンテレフタレートフィルムA’は、供給ロールから巻き戻され、金属板1の片面に接触するようにしてラミネートロール3A、3B間に供給される。金属板1とポリブチレンテレフタレートフィルムA’は、ラミネートロール3A、3Bにより挟み付けられ、ポリエステル樹脂被覆金属板が形成される。
Subsequently, the polybutylene terephthalate film A ′ for forming the polybutylene terephthalate layer A is rewound from the supply roll, and supplied between the laminate rolls 3A and 3B so as to contact one surface of the metal plate 1. The metal plate 1 and the polybutylene terephthalate film A 'are sandwiched between the laminating rolls 3A and 3B to form a polyester resin-coated metal plate.
なお、本実施形態において、ラミネートロールとしては、公知のロールを使用することができる。公知のロールとしては、例えばフッ素ゴム製ロール、あるいはシリコーンゴム製ロール等を挙げることができる。また、ラミネートロールの径は特に制限されるものではないが、例えば200mm~550mmの径のラミネートロールを使用することができる。
In the present embodiment, a known roll can be used as the laminating roll. Known rolls include, for example, fluororubber rolls and silicone rubber rolls. Although the diameter of the laminating roll is not particularly limited, a laminating roll having a diameter of, for example, 200 mm to 550 mm can be used.
また、ラミネートロールの表面温度は、図示しない冷却ロールもしくは加熱ロール等により所定の温度に制御されることが好ましい。ラミネートロールの表面温度としては、製造装置の種類等によっても異なるが、本実施形態においては30℃~180℃とすることが、ポリブチレンテレフタレート層AのX線回折強度比Rの値を好ましい範囲内とするためには好ましい。
It is preferable that the surface temperature of the laminating roll is controlled to a predetermined temperature by a cooling roll or a heating roll (not shown). Although the surface temperature of the laminating roll varies depending on the type of the manufacturing apparatus and the like, in the present embodiment, the temperature is preferably set to 30 ° C. to 180 ° C. in a preferable range of the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A. It is preferable to set it within.
さらに、本実施形態において、ポリエステル樹脂被覆金属板を製造するためのラミネート速度としては、特に制限はされないが一般的には50mpm~300mpmであることが好ましい。
Further, in the present embodiment, the laminating speed for producing the polyester resin-coated metal sheet is not particularly limited, but is generally preferably 50 mpm to 300 mpm.
ここで、ラミネート速度は、ラミネートロールのニップ部の通過時間と関連する。すなわち、ラミネート速度が速い場合にはニップ部の通過時間が短く、ラミネート速度が遅い場合にはニップ部の通過時間が長い。
ニップ部の通過時間はすなわち、ラミネートロールによりポリエステル樹脂被覆金属板が冷却される時間である。したがって、ラミネート速度は、ポリブチレンテレフタレート層AのX線回折強度比Rの値を制御するパラメータのひとつであるといえる。 Here, the laminating speed is related to the transit time of the nip portion of the laminating roll. That is, when the laminating speed is high, the passing time of the nip is short, and when the laminating speed is low, the passing time of the nip is long.
That is, the passage time of the nip portion is a time during which the polyester resin-coated metal plate is cooled by the laminating roll. Therefore, it can be said that the laminating speed is one of the parameters for controlling the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A.
ニップ部の通過時間はすなわち、ラミネートロールによりポリエステル樹脂被覆金属板が冷却される時間である。したがって、ラミネート速度は、ポリブチレンテレフタレート層AのX線回折強度比Rの値を制御するパラメータのひとつであるといえる。 Here, the laminating speed is related to the transit time of the nip portion of the laminating roll. That is, when the laminating speed is high, the passing time of the nip is short, and when the laminating speed is low, the passing time of the nip is long.
That is, the passage time of the nip portion is a time during which the polyester resin-coated metal plate is cooled by the laminating roll. Therefore, it can be said that the laminating speed is one of the parameters for controlling the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A.
本実施形態において、ラミネート速度が50mpm未満の場合、貼り込む直前にフィルムが金属板から輻射熱を受ける時間が長くなり、フィルム皺が発生し易くなるため好ましくない。
一方で、ラミネート速度が300mpmを超える場合は、金属板とフィルムとの間に巻き込まれる気泡の量が大幅に増加するため、耐食性及びレトルト密着性の観点から好ましくない。 In the present embodiment, if the laminating speed is less than 50 mpm, it is not preferable because the time during which the film receives radiant heat from the metal plate immediately before sticking becomes longer and the film wrinkles easily occur.
On the other hand, if the laminating speed exceeds 300 mpm, the amount of air bubbles caught between the metal plate and the film increases significantly, which is not preferable from the viewpoint of corrosion resistance and retort adhesion.
一方で、ラミネート速度が300mpmを超える場合は、金属板とフィルムとの間に巻き込まれる気泡の量が大幅に増加するため、耐食性及びレトルト密着性の観点から好ましくない。 In the present embodiment, if the laminating speed is less than 50 mpm, it is not preferable because the time during which the film receives radiant heat from the metal plate immediately before sticking becomes longer and the film wrinkles easily occur.
On the other hand, if the laminating speed exceeds 300 mpm, the amount of air bubbles caught between the metal plate and the film increases significantly, which is not preferable from the viewpoint of corrosion resistance and retort adhesion.
なお、熱接着の前の段階において、上記ポリブチレンテレフタレートフィルムA’は、上述したように一般的な方法により二軸延伸されていることが好ましい。この二軸延伸フィルムの二軸配向度は、特に制限はされない。
At the stage before the thermal bonding, the polybutylene terephthalate film A ′ is preferably biaxially stretched by a general method as described above. The degree of biaxial orientation of the biaxially stretched film is not particularly limited.
また、図3に示すように、金属板1の両面に同時にフィルムをラミネートして樹脂層を形成してもよい。
その場合、金属板1の両面にポリブチレンテレフタレート層Aを形成してもよい。
あるいは、金属板1の片面にポリブチレンテレフタレート層Aを形成し、他方の面にポリブチレンテレフタレート層Aとは異なるポリエステル樹脂層Bを設けてもよい。その場合、図3に示すように、ポリエステル樹脂層Bとなるポリエステル樹脂フィルムB’を、ポリブチレンテレフタレートフィルムA’と同様にしてラミネートロール3A、3B間で挟み付け、熱接着することができる。 Further, as shown in FIG. 3, a resin layer may be formed by simultaneously laminating films on both surfaces of themetal plate 1.
In that case, the polybutylene terephthalate layer A may be formed on both surfaces of themetal plate 1.
Alternatively, a polybutylene terephthalate layer A may be formed on one side of themetal plate 1 and a polyester resin layer B different from the polybutylene terephthalate layer A may be provided on the other side. In this case, as shown in FIG. 3, the polyester resin film B ′ to be the polyester resin layer B can be sandwiched between the laminating rolls 3A and 3B in the same manner as the polybutylene terephthalate film A ′ and thermally bonded.
その場合、金属板1の両面にポリブチレンテレフタレート層Aを形成してもよい。
あるいは、金属板1の片面にポリブチレンテレフタレート層Aを形成し、他方の面にポリブチレンテレフタレート層Aとは異なるポリエステル樹脂層Bを設けてもよい。その場合、図3に示すように、ポリエステル樹脂層Bとなるポリエステル樹脂フィルムB’を、ポリブチレンテレフタレートフィルムA’と同様にしてラミネートロール3A、3B間で挟み付け、熱接着することができる。 Further, as shown in FIG. 3, a resin layer may be formed by simultaneously laminating films on both surfaces of the
In that case, the polybutylene terephthalate layer A may be formed on both surfaces of the
Alternatively, a polybutylene terephthalate layer A may be formed on one side of the
次に、配向復帰工程について説明する。
図3に示すように、ラミネートロール3A、3Bの下方には、冷却水を収容したクエンチタンク12が設けられている。上記した積層工程の後で、得られたポリエステル樹脂被覆金属板は、クエンチタンク12に送られる。
積層工程における熱により、ポリブチレンテレフタレート樹脂層A中の配向結晶は溶解している。しかしながら、上述したようにポリブチレンテレフタレートのホモポリマーは結晶化速度が非常に速いため、得られたポリエステル樹脂被覆金属板がクエンチタンク12へ送られるまでの間で、崩れた配向結晶が元の配向結晶状態に戻ろうとする現象が発生する(配向復帰)。 Next, the alignment return step will be described.
As shown in FIG. 3, a quenchtank 12 containing cooling water is provided below the laminating rolls 3A and 3B. After the above-described laminating step, the obtained polyester resin-coated metal sheet is sent to the quench tank 12.
The oriented crystals in the polybutylene terephthalate resin layer A are dissolved by the heat in the laminating step. However, as described above, since the homopolymer of polybutylene terephthalate has a very high crystallization rate, the collapsed oriented crystal loses its original orientation until the obtained polyester resin-coated metal plate is sent to the quenchtank 12. A phenomenon of returning to the crystalline state occurs (orientation return).
図3に示すように、ラミネートロール3A、3Bの下方には、冷却水を収容したクエンチタンク12が設けられている。上記した積層工程の後で、得られたポリエステル樹脂被覆金属板は、クエンチタンク12に送られる。
積層工程における熱により、ポリブチレンテレフタレート樹脂層A中の配向結晶は溶解している。しかしながら、上述したようにポリブチレンテレフタレートのホモポリマーは結晶化速度が非常に速いため、得られたポリエステル樹脂被覆金属板がクエンチタンク12へ送られるまでの間で、崩れた配向結晶が元の配向結晶状態に戻ろうとする現象が発生する(配向復帰)。 Next, the alignment return step will be described.
As shown in FIG. 3, a quench
The oriented crystals in the polybutylene terephthalate resin layer A are dissolved by the heat in the laminating step. However, as described above, since the homopolymer of polybutylene terephthalate has a very high crystallization rate, the collapsed oriented crystal loses its original orientation until the obtained polyester resin-coated metal plate is sent to the quench
本実施形態においては、この配向復帰が生じる時間Tを、積層直後からクエンチタンクの冷却水に入るまでの時間と定義する。より具体的には、図3に示すように、ポリエステル樹脂被覆金属板の任意の箇所Pが、ラミネートロールのニップ部を脱した直後のX地点から、クエンチタンク12の冷却水に入るまでのY地点に移動するのに要する時間と定義する。
に お い て In the present embodiment, the time T at which the orientation is returned is defined as the time from immediately after lamination to the time when the cooling water of the quench tank enters. More specifically, as shown in FIG. 3, the Y from the point X immediately after the arbitrary point P of the polyester resin-coated metal plate has come out of the nip portion of the laminating roll to the point at which the cooling water of the quench tank 12 enters is removed. Defined as the time required to move to a point.
そして、本実施形態においては、この配向復帰が生じる時間Tを3秒以下とすることが好ましい。
配向復帰が生じる時間Tが3秒を超える場合、上述した配向復帰が大きくなりすぎるため、本実施形態の特徴であるX線回折強度比Rを好ましい値に制御することが困難となる。
従って、本実施形態においては、時間Tを3秒以下とすることが好ましいといえる。 In the present embodiment, it is preferable that the time T during which the alignment return occurs is 3 seconds or less.
If the time T during which the orientation return occurs exceeds 3 seconds, the above-described orientation return becomes too large, and it becomes difficult to control the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, to a preferable value.
Therefore, in the present embodiment, it can be said that the time T is preferably set to 3 seconds or less.
配向復帰が生じる時間Tが3秒を超える場合、上述した配向復帰が大きくなりすぎるため、本実施形態の特徴であるX線回折強度比Rを好ましい値に制御することが困難となる。
従って、本実施形態においては、時間Tを3秒以下とすることが好ましいといえる。 In the present embodiment, it is preferable that the time T during which the alignment return occurs is 3 seconds or less.
If the time T during which the orientation return occurs exceeds 3 seconds, the above-described orientation return becomes too large, and it becomes difficult to control the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, to a preferable value.
Therefore, in the present embodiment, it can be said that the time T is preferably set to 3 seconds or less.
次に、本実施形態における急冷工程について説明する。
上述したように、図3に示されるように、ラミネートロール3A、3Bの下方には、冷却水を収容したクエンチタンク12が設けられている。得られたポリエステル樹脂被覆金属板は、このクエンチタンク12に送られ、直ちに80℃以下に急冷されることが、本実施形態の特徴であるX線回折強度比Rを好ましい値に制御するためには好ましい。
冷却温度が80℃を超える場合、冷却後も配向復帰が進んでしまい、本実施形態の特徴であるX線回折強度比Rの値を好ましい範囲に制御することができない可能性があるため、好ましくない。 Next, the quenching step in the present embodiment will be described.
As described above, the quenchtank 12 containing cooling water is provided below the laminating rolls 3A and 3B, as shown in FIG. The obtained polyester resin-coated metal sheet is sent to the quench tank 12 and immediately quenched to 80 ° C. or less, in order to control the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, to a preferable value. Is preferred.
If the cooling temperature is higher than 80 ° C., the orientation return proceeds even after cooling, and the value of the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, may not be able to be controlled to a preferable range. Absent.
上述したように、図3に示されるように、ラミネートロール3A、3Bの下方には、冷却水を収容したクエンチタンク12が設けられている。得られたポリエステル樹脂被覆金属板は、このクエンチタンク12に送られ、直ちに80℃以下に急冷されることが、本実施形態の特徴であるX線回折強度比Rを好ましい値に制御するためには好ましい。
冷却温度が80℃を超える場合、冷却後も配向復帰が進んでしまい、本実施形態の特徴であるX線回折強度比Rの値を好ましい範囲に制御することができない可能性があるため、好ましくない。 Next, the quenching step in the present embodiment will be described.
As described above, the quench
If the cooling temperature is higher than 80 ° C., the orientation return proceeds even after cooling, and the value of the X-ray diffraction intensity ratio R, which is a feature of the present embodiment, may not be able to be controlled to a preferable range. Absent.
上述したように、本実施形態においては、(a)熱接着前の金属板1の温度、(b)ラミネートロールの表面温度、(c)ラミネートロールニップ部における冷却時間(d)配向復帰が生じる時間T、の各パラメータを最適な値にすることにより、ポリブチレンテレフタレート層Aの配向結晶の状態を制御することを特徴とする。
As described above, in the present embodiment, (a) the temperature of the metal plate 1 before the thermal bonding, (b) the surface temperature of the laminating roll, (c) the cooling time at the laminating roll nip portion, and (d) the orientation return occurs. The state of the oriented crystal of the polybutylene terephthalate layer A is controlled by setting each parameter of the time T to an optimum value.
そして、ポリブチレンテレフタレート層AのX線回折強度比Rの値を規定の範囲内とすることにより、好ましい耐衝撃性・成形性・レトルト密着性・レトルトブラッシング耐性を兼ね備えたポリエステル樹脂被覆金属板を得るものである。
Then, by setting the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A within the specified range, a polyester resin-coated metal plate having preferable impact resistance, moldability, retort adhesion, and retort brushing resistance is obtained. What you get.
[容器]
次に、本実施形態における金属缶等の容器について説明する。
本実施形態における容器としては、飲料缶や食品缶等の金属缶、角形缶、一斗缶、ドラム缶、バッテリーケース、パウチ等を例示することができるが、これらに限られるものではない。 [container]
Next, a container such as a metal can in this embodiment will be described.
Examples of the container in the present embodiment include, but are not limited to, metal cans such as beverage cans and food cans, square cans, cans, drums, battery cases, and pouches.
次に、本実施形態における金属缶等の容器について説明する。
本実施形態における容器としては、飲料缶や食品缶等の金属缶、角形缶、一斗缶、ドラム缶、バッテリーケース、パウチ等を例示することができるが、これらに限られるものではない。 [container]
Next, a container such as a metal can in this embodiment will be described.
Examples of the container in the present embodiment include, but are not limited to, metal cans such as beverage cans and food cans, square cans, cans, drums, battery cases, and pouches.
本実施形態の容器は、上記したポリエステル樹脂被覆金属板を用いて公知の製缶方法により製缶される。公知の製缶方法としては、例えば、絞り加工、絞りしごき加工、ストレッチドロー&アイアニング加工、等が挙げられる。
容器 The container of the present embodiment is manufactured by a known can manufacturing method using the above-described polyester resin-coated metal plate. Known methods for making cans include, for example, drawing, drawing and ironing, stretch draw and ironing, and the like.
本実施形態の容器においては、外面に上記したポリブチレンテレフタレート層Aが形成されていることが、レトルトブラッシング(白斑)の発生を抑制する観点からは好ましい。
容器 In the container of the present embodiment, it is preferable that the above-mentioned polybutylene terephthalate layer A is formed on the outer surface from the viewpoint of suppressing the occurrence of retort brushing (white spots).
なお、本実施形態においては、容器の外面及び内面の両面において、ポリブチレンテレフタレート層Aが積層されていてもよい。
あるいは、容器の外面には上記したポリブチレンテレフタレート層Aが形成され、内面には上記したポリエステル樹脂層Bが積層されていてもよい。 In this embodiment, the polybutylene terephthalate layer A may be laminated on both the outer surface and the inner surface of the container.
Alternatively, the above-mentioned polybutylene terephthalate layer A may be formed on the outer surface of the container, and the above-mentioned polyester resin layer B may be laminated on the inner surface.
あるいは、容器の外面には上記したポリブチレンテレフタレート層Aが形成され、内面には上記したポリエステル樹脂層Bが積層されていてもよい。 In this embodiment, the polybutylene terephthalate layer A may be laminated on both the outer surface and the inner surface of the container.
Alternatively, the above-mentioned polybutylene terephthalate layer A may be formed on the outer surface of the container, and the above-mentioned polyester resin layer B may be laminated on the inner surface.
[容器蓋]
本実施形態における容器蓋としては、いわゆるステイ・オン・タブタイプのSOT缶蓋や、フルオープンタイプのイージーオープン缶蓋(EOE)が挙げられる。または、3ピース缶の天地蓋を挙げることもできる。これらの缶蓋も、公知の方法により製造することができる。 [Container lid]
Examples of the container lid in the present embodiment include a so-called stay-on-tab type SOT can lid and a full open type easy open can lid (EOE). Alternatively, a three-piece can roof can be mentioned. These can lids can also be manufactured by a known method.
本実施形態における容器蓋としては、いわゆるステイ・オン・タブタイプのSOT缶蓋や、フルオープンタイプのイージーオープン缶蓋(EOE)が挙げられる。または、3ピース缶の天地蓋を挙げることもできる。これらの缶蓋も、公知の方法により製造することができる。 [Container lid]
Examples of the container lid in the present embodiment include a so-called stay-on-tab type SOT can lid and a full open type easy open can lid (EOE). Alternatively, a three-piece can roof can be mentioned. These can lids can also be manufactured by a known method.
本実施形態の容器蓋においては、外面に上記したポリブチレンテレフタレート層Aが形成されていることが、レトルトブラッシング(白斑)の発生を抑制する観点からは好ましい。
容器 In the container lid of the present embodiment, it is preferable that the above-mentioned polybutylene terephthalate layer A is formed on the outer surface from the viewpoint of suppressing the occurrence of retort brushing (white spots).
なお、容器蓋の外面及び内面に、上記したポリブチレンテレフタレート層Aが積層されていてもよい。あるいは、容器蓋の内面には、ポリエステル樹脂層Bが積層されていてもよいし、図示しない塗膜が形成されていてもよい。
The above-mentioned polybutylene terephthalate layer A may be laminated on the outer and inner surfaces of the container lid. Alternatively, a polyester resin layer B may be laminated on the inner surface of the container lid, or a coating film (not shown) may be formed.
以下、本発明を実施例によりさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.
[ポリエステル樹脂被覆金属板の作製]
金属板としては、板厚0.225mmのティンフリースチール(TFS)板を使用した。 [Production of polyester resin coated metal plate]
As the metal plate, a tin-free steel (TFS) plate having a thickness of 0.225 mm was used.
金属板としては、板厚0.225mmのティンフリースチール(TFS)板を使用した。 [Production of polyester resin coated metal plate]
As the metal plate, a tin-free steel (TFS) plate having a thickness of 0.225 mm was used.
(実施例1)
ポリブチレンテレフタレート層Aとして、厚み15μmの興人フィルム&ケミカルズ(株)の二軸延伸ポリブチレンテレフタレートフィルム(商品名BOBLET)を用意した。 (Example 1)
As the polybutylene terephthalate layer A, a biaxially stretched polybutylene terephthalate film (trade name: BOBLET) having a thickness of 15 μm from Kojin Film & Chemicals Co., Ltd. was prepared.
ポリブチレンテレフタレート層Aとして、厚み15μmの興人フィルム&ケミカルズ(株)の二軸延伸ポリブチレンテレフタレートフィルム(商品名BOBLET)を用意した。 (Example 1)
As the polybutylene terephthalate layer A, a biaxially stretched polybutylene terephthalate film (trade name: BOBLET) having a thickness of 15 μm from Kojin Film & Chemicals Co., Ltd. was prepared.
次に、興人フィルム&ケミカルズ(株)のBOBLET・15μmを、260℃に加熱した金属板の両面に接触させ、1対のラミネートロールの間で挟みつけて圧着して積層し、ポリエステル樹脂被覆金属板を作製した。なお、ラミネートロールとしてはフッ素ゴム製ロールを使用し、その表面温度は180℃とした。また、ラミネート速度は55mpm(meter per minute)とした。
Next, BOBLET 15 μm made by Kojin Film & Chemicals Co., Ltd. was brought into contact with both sides of a metal plate heated to 260 ° C., sandwiched between a pair of laminating rolls, pressed and laminated, and coated with a polyester resin. A metal plate was produced. In addition, a roll made of fluororubber was used as a laminating roll, and its surface temperature was 180 ° C. The laminating speed was 55 mpm (meter @ per @ minute).
得られたポリエステル樹脂被覆金属板は、直ちに冷却水を収容したクエンチタンクに送られ冷却された。なお、冷却水の温度は50℃であり、クエンチタンク内で冷却された後のポリエステル樹脂被覆金属板温度は50℃であった。また、配向復帰が生じる時間Tは3秒であった。
ポ リ エ ス テ ル The obtained polyester resin-coated metal plate was immediately sent to a quench tank containing cooling water and cooled. The temperature of the cooling water was 50 ° C, and the temperature of the polyester resin-coated metal plate after cooling in the quench tank was 50 ° C. In addition, the time T during which the alignment return occurred was 3 seconds.
得られたポリエステル樹脂被覆金属板のポリブチレンテレフタレート層AのX線回折強度比を算出した。X線回折の測定条件は下記のとおりとした。
X The X-ray diffraction intensity ratio of the polybutylene terephthalate layer A of the obtained polyester resin-coated metal plate was calculated. The measurement conditions of X-ray diffraction were as follows.
(X線回折によるX線回折強度比の算出)
X線回折装置:株式会社リガク製、RINT-2500
X線 :CuKαX線(波長λ=0.1542nm)
管電圧 :40kV
管電流 :200mA
発散スリット:1/2°
受光スリット:0.15mm (Calculation of X-ray diffraction intensity ratio by X-ray diffraction)
X-ray diffractometer: RINT-2500, manufactured by Rigaku Corporation
X-ray: CuKα X-ray (wavelength λ = 0.1542 nm)
Tube voltage: 40kV
Tube current: 200mA
Divergence slit: 1/2 °
Light receiving slit: 0.15mm
X線回折装置:株式会社リガク製、RINT-2500
X線 :CuKαX線(波長λ=0.1542nm)
管電圧 :40kV
管電流 :200mA
発散スリット:1/2°
受光スリット:0.15mm (Calculation of X-ray diffraction intensity ratio by X-ray diffraction)
X-ray diffractometer: RINT-2500, manufactured by Rigaku Corporation
X-ray: CuKα X-ray (wavelength λ = 0.1542 nm)
Tube voltage: 40kV
Tube current: 200mA
Divergence slit: 1/2 °
Light receiving slit: 0.15mm
得られたX線回折スペクトルを図4に示す。図4に示されるように、(100)面のX線回折強度としては、2θ=23.0~24.0°の範囲内に確認される最大値である3800cpsを採用した。また、(1-11)面のX線回折強度としては、2θ=25.0°~26.0°の範囲内に確認される最大値である1900cpsを採用した。なお、バックグラウンド補正は行わなかった(他の実施例及び比較例でも同様)。
「(100)面の回折強度/(1-11)面の回折強度」の計算により、X線回折強度比R=2.0の値を得た。結果を表1に示す。 FIG. 4 shows the obtained X-ray diffraction spectrum. As shown in FIG. 4, as the X-ray diffraction intensity of the (100) plane, 3800 cps, which is the maximum value found in the range of 2θ = 23.0 to 24.0 °, was employed. As the X-ray diffraction intensity of the (1-11) plane, 1900 cps, which is the maximum value found in the range of 2θ = 25.0 ° to 26.0 °, was used. The background correction was not performed (the same applies to other examples and comparative examples).
By the calculation of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”, a value of X-ray diffraction intensity ratio R = 2.0 was obtained. Table 1 shows the results.
「(100)面の回折強度/(1-11)面の回折強度」の計算により、X線回折強度比R=2.0の値を得た。結果を表1に示す。 FIG. 4 shows the obtained X-ray diffraction spectrum. As shown in FIG. 4, as the X-ray diffraction intensity of the (100) plane, 3800 cps, which is the maximum value found in the range of 2θ = 23.0 to 24.0 °, was employed. As the X-ray diffraction intensity of the (1-11) plane, 1900 cps, which is the maximum value found in the range of 2θ = 25.0 ° to 26.0 °, was used. The background correction was not performed (the same applies to other examples and comparative examples).
By the calculation of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”, a value of X-ray diffraction intensity ratio R = 2.0 was obtained. Table 1 shows the results.
(耐衝撃性評価)
上記のようにして得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ塗布し、ポリブチレンテレフタレート層Aが缶外面となるようにして直径142mmの円板(ブランク)に打抜くと同時に絞り加工により1stカップを作製した。作製した1stカップに再絞り加工を行い、絞り比2.15のDRD(Draw and Redraw)カップを作製した。 (Evaluation of impact resistance)
A paraffin wax is applied to the polyester resin-coated metal plate obtained as described above at a rate of 50 mg / m 2 on one side, and the polybutylene terephthalate layer A is applied to a disk (blank) having a diameter of 142 mm so as to be the outer surface of the can. At the same time as the removal, a 1st cup was prepared by drawing. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
上記のようにして得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ塗布し、ポリブチレンテレフタレート層Aが缶外面となるようにして直径142mmの円板(ブランク)に打抜くと同時に絞り加工により1stカップを作製した。作製した1stカップに再絞り加工を行い、絞り比2.15のDRD(Draw and Redraw)カップを作製した。 (Evaluation of impact resistance)
A paraffin wax is applied to the polyester resin-coated metal plate obtained as described above at a rate of 50 mg / m 2 on one side, and the polybutylene terephthalate layer A is applied to a disk (blank) having a diameter of 142 mm so as to be the outer surface of the can. At the same time as the removal, a 1st cup was prepared by drawing. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
得られたカップに上端部までイオン交換水を入れ、125℃で45分間のレトルト殺菌処理を実施した。
次いで、カップの底から40mmの高さ位置にデュポン衝撃試験機を用いて高さ50mmから172gの重りをポンチ(先端R=0.5mm)に落下させ、デントを付与した。なお、デント付与箇所は、板の圧延方向、45°方向、直角方向の3か所とした。
その後、デント部のERV(Enamel Rater Value)を測定した。測定に際しては、指定の電解液(1%NaCl+界面活性剤(ラピゾール、日本油脂製)・200mg/L)を2:1の割合でエタノールにより希釈した液を用いた。6.3Vの電圧を印可し、4秒後の電流値を測定し、以下のように評価を行った。
◎ ・・・ 0.005mA以下、
○ ・・・ 0.005mAを超え0.05mA以下、
△ ・・・ 0.05mAを超え0.5mA以下、
× ・・・ 0.5mA超え Ion-exchanged water was put into the obtained cup up to the upper end, and a retort sterilization treatment was performed at 125 ° C. for 45 minutes.
Next, a weight of 172 g from a height of 50 mm was dropped on a punch (tip R = 0.5 mm) at a height of 40 mm from the bottom of the cup using a Dupont impact tester to give a dent. The dents were provided at three locations: the rolling direction of the sheet, the 45 ° direction, and the perpendicular direction.
Thereafter, the ERV (Enamel Rate Value) of the dent portion was measured. At the time of measurement, a solution obtained by diluting a specified electrolytic solution (1% NaCl + surfactant (rapizol, manufactured by NOF Corporation) 200 mg / L) with ethanol at a ratio of 2: 1 was used. A voltage of 6.3 V was applied, the current value after 4 seconds was measured, and evaluation was performed as follows.
◎ ... 0.005mA or less
: More than 0.005 mA and 0.05 mA or less,
△ ・ ・ ・ More than 0.05mA and 0.5mA or less,
× ・ ・ ・ Over 0.5mA
次いで、カップの底から40mmの高さ位置にデュポン衝撃試験機を用いて高さ50mmから172gの重りをポンチ(先端R=0.5mm)に落下させ、デントを付与した。なお、デント付与箇所は、板の圧延方向、45°方向、直角方向の3か所とした。
その後、デント部のERV(Enamel Rater Value)を測定した。測定に際しては、指定の電解液(1%NaCl+界面活性剤(ラピゾール、日本油脂製)・200mg/L)を2:1の割合でエタノールにより希釈した液を用いた。6.3Vの電圧を印可し、4秒後の電流値を測定し、以下のように評価を行った。
◎ ・・・ 0.005mA以下、
○ ・・・ 0.005mAを超え0.05mA以下、
△ ・・・ 0.05mAを超え0.5mA以下、
× ・・・ 0.5mA超え Ion-exchanged water was put into the obtained cup up to the upper end, and a retort sterilization treatment was performed at 125 ° C. for 45 minutes.
Next, a weight of 172 g from a height of 50 mm was dropped on a punch (tip R = 0.5 mm) at a height of 40 mm from the bottom of the cup using a Dupont impact tester to give a dent. The dents were provided at three locations: the rolling direction of the sheet, the 45 ° direction, and the perpendicular direction.
Thereafter, the ERV (Enamel Rate Value) of the dent portion was measured. At the time of measurement, a solution obtained by diluting a specified electrolytic solution (1% NaCl + surfactant (rapizol, manufactured by NOF Corporation) 200 mg / L) with ethanol at a ratio of 2: 1 was used. A voltage of 6.3 V was applied, the current value after 4 seconds was measured, and evaluation was performed as follows.
◎ ... 0.005mA or less
: More than 0.005 mA and 0.05 mA or less,
△ ・ ・ ・ More than 0.05mA and 0.5mA or less,
× ・ ・ ・ Over 0.5mA
(成形性評価)
得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ両面に塗布した。直径151mmの円板(ブランク)に打ち抜いた後、ポリブチレンテレフタレート層Aが缶外面となるようにして、絞り加工を行い1stカップに加工した。続いてB/M(Body Maker)にてリダクション率45%のDI缶(7号缶)に200cpmの速度で製缶し、缶外面の削れの発生の有無を確認した。
結果を以下のように評価した。
○ ・・・ 外面削れの発生無く、実機生産が可能なレベル。
× ・・・ 外面削れが発生しており、実機生産は困難なレベル。 (Formability evaluation)
Paraffin wax was applied to both sides of the obtained polyester resin-coated metal plate at 50 mg / m 2 on each side. After punching into a disk (blank) having a diameter of 151 mm, drawing was performed so that the polybutylene terephthalate layer A became the outer surface of the can, and processed into a 1st cup. Subsequently, a B / M (Body Maker) was used to make a DI can (No. 7 can) with a reduction ratio of 45% at a speed of 200 cpm, and it was confirmed whether or not the outer surface of the can was shaved.
The results were evaluated as follows.
○ ・ ・ ・ At the level where actual production can be performed without external shavings.
×: The level of production of the actual machine is difficult due to the occurrence of external scraping.
得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ両面に塗布した。直径151mmの円板(ブランク)に打ち抜いた後、ポリブチレンテレフタレート層Aが缶外面となるようにして、絞り加工を行い1stカップに加工した。続いてB/M(Body Maker)にてリダクション率45%のDI缶(7号缶)に200cpmの速度で製缶し、缶外面の削れの発生の有無を確認した。
結果を以下のように評価した。
○ ・・・ 外面削れの発生無く、実機生産が可能なレベル。
× ・・・ 外面削れが発生しており、実機生産は困難なレベル。 (Formability evaluation)
Paraffin wax was applied to both sides of the obtained polyester resin-coated metal plate at 50 mg / m 2 on each side. After punching into a disk (blank) having a diameter of 151 mm, drawing was performed so that the polybutylene terephthalate layer A became the outer surface of the can, and processed into a 1st cup. Subsequently, a B / M (Body Maker) was used to make a DI can (No. 7 can) with a reduction ratio of 45% at a speed of 200 cpm, and it was confirmed whether or not the outer surface of the can was shaved.
The results were evaluated as follows.
○ ・ ・ ・ At the level where actual production can be performed without external shavings.
×: The level of production of the actual machine is difficult due to the occurrence of external scraping.
(レトルト密着性評価)
得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ塗布し、ポリブチレンテレフタレート層Aが缶外面となるようにして直径142mmの円板(ブランク)に打抜くと同時に絞り加工により1stカップを作製した。作製した1stカップに再絞り加工を行い、絞り比2.15のDRD(Draw and Redraw)カップを作製した。 (Evaluation of retort adhesion)
A paraffin wax is applied to the obtained polyester resin-coated metal plate at a rate of 50 mg / m 2 on each side, and punched into a disk (blank) having a diameter of 142 mm so that the polybutylene terephthalate layer A becomes the outer surface of the can. Produced the 1st cup. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ塗布し、ポリブチレンテレフタレート層Aが缶外面となるようにして直径142mmの円板(ブランク)に打抜くと同時に絞り加工により1stカップを作製した。作製した1stカップに再絞り加工を行い、絞り比2.15のDRD(Draw and Redraw)カップを作製した。 (Evaluation of retort adhesion)
A paraffin wax is applied to the obtained polyester resin-coated metal plate at a rate of 50 mg / m 2 on each side, and punched into a disk (blank) having a diameter of 142 mm so that the polybutylene terephthalate layer A becomes the outer surface of the can. Produced the 1st cup. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
得られたカップの外側に底から高さ25mm及び50mm位置にカッターで全周に切れ目を入れた。水を張った容器にカップを沈め、125℃で45分間のレトルト殺菌処理を実施した。前記切れ目の部分における、フィルムの最大剥離長さを測定した。評価は以下のように行った。
◎ ・・・ 剥離長さが5mm以下
○ ・・・ 剥離長さが5mmを超え10mm以下
△ ・・・ 剥離長さが10mmを超え15mm以下
× ・・・ 剥離長さが15mmを超え20mm以下
×× ・・・ 剥離長さが20mmを超える Cuts were made on the entire circumference of the obtained cup with a cutter at positions 25 mm and 50 mm above the bottom from the bottom. The cup was submerged in a container filled with water and subjected to a retort sterilization treatment at 125 ° C. for 45 minutes. The maximum peel length of the film at the cut was measured. The evaluation was performed as follows.
◎ ・ ・ ・ Peel length is 5mm or less ○ ・ ・ ・ Peel length is more than 5mm and 10mm or less △ ・ ・ ・ Peel length is more than 10mm and 15mm or less × ・ ・ ・ Peel length is more than 15mm and 20mm or less × ×: The peel length exceeds 20 mm
◎ ・・・ 剥離長さが5mm以下
○ ・・・ 剥離長さが5mmを超え10mm以下
△ ・・・ 剥離長さが10mmを超え15mm以下
× ・・・ 剥離長さが15mmを超え20mm以下
×× ・・・ 剥離長さが20mmを超える Cuts were made on the entire circumference of the obtained cup with a cutter at positions 25 mm and 50 mm above the bottom from the bottom. The cup was submerged in a container filled with water and subjected to a retort sterilization treatment at 125 ° C. for 45 minutes. The maximum peel length of the film at the cut was measured. The evaluation was performed as follows.
◎ ・ ・ ・ Peel length is 5mm or less ○ ・ ・ ・ Peel length is more than 5mm and 10mm or less △ ・ ・ ・ Peel length is more than 10mm and 15mm or less × ・ ・ ・ Peel length is more than 15mm and 20mm or less × ×: The peel length exceeds 20 mm
(レトルトブラッシング評価)
得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ塗布し、ポリブチレンテレフタレート層Aが缶外面となるようにして直径142mmの円板(ブランク)に打抜くと同時に絞り加工により1stカップを作製した。作製した1stカップに再絞り加工を行い、絞り比2.15のDRD(Draw and Redraw)カップを作製した。 (Retort brushing evaluation)
A paraffin wax is applied to the obtained polyester resin-coated metal plate at a rate of 50 mg / m 2 on each side, and punched into a disk (blank) having a diameter of 142 mm so that the polybutylene terephthalate layer A becomes the outer surface of the can. Produced the 1st cup. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
得られたポリエステル樹脂被覆金属板に、パラフィンワックスを片面50mg/m2ずつ塗布し、ポリブチレンテレフタレート層Aが缶外面となるようにして直径142mmの円板(ブランク)に打抜くと同時に絞り加工により1stカップを作製した。作製した1stカップに再絞り加工を行い、絞り比2.15のDRD(Draw and Redraw)カップを作製した。 (Retort brushing evaluation)
A paraffin wax is applied to the obtained polyester resin-coated metal plate at a rate of 50 mg / m 2 on each side, and punched into a disk (blank) having a diameter of 142 mm so that the polybutylene terephthalate layer A becomes the outer surface of the can. Produced the 1st cup. The produced 1st cup was subjected to redrawing to prepare a DRD (Draw and Reddraw) cup having a drawing ratio of 2.15.
得られたカップにイオン交換水120mlを入れ、当該カップをSUS製のパンチングメタル(穴径Φ=5mm)容器に入れ、昇温速度が40℃/minのレトルト釜にて125℃で10分間のレトルト殺菌処理を実施した。取り出した缶を以下の基準により5段階で評価した。
××・・・パンチ穴がカップ底部の全面に転写
× ・・・パンチ穴がカップ底部のほぼ全面に転写(8割程度)
△ ・・・半数のパンチ穴がカップ底部に転写
○ ・・・わずかにパンチ穴がカップ底部に転写(2割以下)
◎ ・・・カップ底部にパンチ穴の転写無し
以上で得られた結果を、表1に示す。 120 ml of ion-exchanged water is put into the obtained cup, the cup is put into a SUS punching metal (hole diameter Φ = 5 mm) container, and the temperature is raised at 125 ° C. for 10 minutes in a retort pot having a temperature rising rate of 40 ° C./min. A retort sterilization treatment was performed. The taken out cans were evaluated on a 5-point scale according to the following criteria.
XX: Punch holes are transferred to the entire surface of the cup bottom. X: Punch holes are transferred to almost the entire bottom of the cup (about 80%).
△ ・ ・ ・ Half of the punch holes are transferred to the bottom of the cup ○ ・ ・ ・ Slight punch holes are transferred to the bottom of the cup (less than 20%)
A: No transfer of punch holes on the bottom of the cup The results obtained above are shown in Table 1.
××・・・パンチ穴がカップ底部の全面に転写
× ・・・パンチ穴がカップ底部のほぼ全面に転写(8割程度)
△ ・・・半数のパンチ穴がカップ底部に転写
○ ・・・わずかにパンチ穴がカップ底部に転写(2割以下)
◎ ・・・カップ底部にパンチ穴の転写無し
以上で得られた結果を、表1に示す。 120 ml of ion-exchanged water is put into the obtained cup, the cup is put into a SUS punching metal (hole diameter Φ = 5 mm) container, and the temperature is raised at 125 ° C. for 10 minutes in a retort pot having a temperature rising rate of 40 ° C./min. A retort sterilization treatment was performed. The taken out cans were evaluated on a 5-point scale according to the following criteria.
XX: Punch holes are transferred to the entire surface of the cup bottom. X: Punch holes are transferred to almost the entire bottom of the cup (about 80%).
△ ・ ・ ・ Half of the punch holes are transferred to the bottom of the cup ○ ・ ・ ・ Slight punch holes are transferred to the bottom of the cup (less than 20%)
A: No transfer of punch holes on the bottom of the cup The results obtained above are shown in Table 1.
(実施例2)
ラミネートロールの表面温度を150℃とした以外は実施例1と同様にして行った。
得られたX線回折ピークのチャートを図5に示す。図5に示されるように、(100)面のX線回折強度としては、2θ=23.0~24.0°の範囲内に確認される最大値である7500cpsを採用した。また、(1-11)面のX線回折強度としては、2θ=25.0°~26.0°の範囲内に確認される最大値である2080cpsを採用した。
「(100)面の回折強度/(1-11)面の回折強度」の計算により、X線回折強度比R=3.6の値を得た。結果を表1に示す。 (Example 2)
The operation was performed in the same manner as in Example 1 except that the surface temperature of the laminating roll was set to 150 ° C.
FIG. 5 shows a chart of the obtained X-ray diffraction peak. As shown in FIG. 5, as the X-ray diffraction intensity of the (100) plane, 7500 cps, which is the maximum value found in the range of 2θ = 23.0 to 24.0 °, was adopted. As the X-ray diffraction intensity of the (1-11) plane, 2080 cps, which is the maximum value confirmed in the range of 2θ = 25.0 ° to 26.0 °, was employed.
By the calculation of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”, an X-ray diffraction intensity ratio R = 3.6 was obtained. Table 1 shows the results.
ラミネートロールの表面温度を150℃とした以外は実施例1と同様にして行った。
得られたX線回折ピークのチャートを図5に示す。図5に示されるように、(100)面のX線回折強度としては、2θ=23.0~24.0°の範囲内に確認される最大値である7500cpsを採用した。また、(1-11)面のX線回折強度としては、2θ=25.0°~26.0°の範囲内に確認される最大値である2080cpsを採用した。
「(100)面の回折強度/(1-11)面の回折強度」の計算により、X線回折強度比R=3.6の値を得た。結果を表1に示す。 (Example 2)
The operation was performed in the same manner as in Example 1 except that the surface temperature of the laminating roll was set to 150 ° C.
FIG. 5 shows a chart of the obtained X-ray diffraction peak. As shown in FIG. 5, as the X-ray diffraction intensity of the (100) plane, 7500 cps, which is the maximum value found in the range of 2θ = 23.0 to 24.0 °, was adopted. As the X-ray diffraction intensity of the (1-11) plane, 2080 cps, which is the maximum value confirmed in the range of 2θ = 25.0 ° to 26.0 °, was employed.
By the calculation of “(100) plane diffraction intensity / (1-11) plane diffraction intensity”, an X-ray diffraction intensity ratio R = 3.6 was obtained. Table 1 shows the results.
(実施例3)
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間T、を各々表1に示すものとした以外は、実施例1と同様にして行った。 (Example 3)
The procedure was performed in the same manner as in Example 1 except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1.
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間T、を各々表1に示すものとした以外は、実施例1と同様にして行った。 (Example 3)
The procedure was performed in the same manner as in Example 1 except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1.
(実施例4)
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間T、を各々表1に示すものとした以外は、実施例1と同様にして行った。 (Example 4)
The procedure was performed in the same manner as in Example 1 except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1.
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間T、を各々表1に示すものとした以外は、実施例1と同様にして行った。 (Example 4)
The procedure was performed in the same manner as in Example 1 except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1.
(実施例5)
ポリブチレンテレフタレート層Aを形成する二軸延伸ポリブチレンテレフタレートフィルムの厚さを25μmとし、ラミネート前の金属板の加熱温度を275℃、ラミネートロールの表面温度を150℃とした以外は、実施例1と同様にして行った。 (Example 5)
Example 1 Example 1 was repeated except that the thickness of the biaxially stretched polybutylene terephthalate film forming the polybutylene terephthalate layer A was 25 μm, the heating temperature of the metal plate before lamination was 275 ° C., and the surface temperature of the laminating roll was 150 ° C. Was performed in the same manner as described above.
ポリブチレンテレフタレート層Aを形成する二軸延伸ポリブチレンテレフタレートフィルムの厚さを25μmとし、ラミネート前の金属板の加熱温度を275℃、ラミネートロールの表面温度を150℃とした以外は、実施例1と同様にして行った。 (Example 5)
Example 1 Example 1 was repeated except that the thickness of the biaxially stretched polybutylene terephthalate film forming the polybutylene terephthalate layer A was 25 μm, the heating temperature of the metal plate before lamination was 275 ° C., and the surface temperature of the laminating roll was 150 ° C. Was performed in the same manner as described above.
(実施例6)
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tを各々表1に示すものとした以外は、実施例5と同様にして行った。 (Example 6)
The procedure was performed in the same manner as in Example 5, except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was returned were as shown in Table 1.
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tを各々表1に示すものとした以外は、実施例5と同様にして行った。 (Example 6)
The procedure was performed in the same manner as in Example 5, except that the heating temperature of the metal plate before lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was returned were as shown in Table 1.
(比較例1)
ラミネート前の金属板の加熱温度を235℃、ラミネートロールの表面温度を165℃とした以外は、実施例1と同様にして行った。 (Comparative Example 1)
Example 1 was repeated except that the heating temperature of the metal plate before lamination was 235 ° C and the surface temperature of the laminating roll was 165 ° C.
ラミネート前の金属板の加熱温度を235℃、ラミネートロールの表面温度を165℃とした以外は、実施例1と同様にして行った。 (Comparative Example 1)
Example 1 was repeated except that the heating temperature of the metal plate before lamination was 235 ° C and the surface temperature of the laminating roll was 165 ° C.
(比較例2)
ラミネート速度を40mpm、ラミネート前の金属板の加熱温度を240℃、ラミネートロールの表面温度を150℃、及び配向復帰が生じる時間Tを4秒とした以外は、実施例1と同様にして行った。 (Comparative Example 2)
The procedure was performed in the same manner as in Example 1 except that the laminating speed was 40 mpm, the heating temperature of the metal plate before laminating was 240 ° C., the surface temperature of the laminating roll was 150 ° C., and the time T during which the orientation return occurred was 4 seconds. .
ラミネート速度を40mpm、ラミネート前の金属板の加熱温度を240℃、ラミネートロールの表面温度を150℃、及び配向復帰が生じる時間Tを4秒とした以外は、実施例1と同様にして行った。 (Comparative Example 2)
The procedure was performed in the same manner as in Example 1 except that the laminating speed was 40 mpm, the heating temperature of the metal plate before laminating was 240 ° C., the surface temperature of the laminating roll was 150 ° C., and the time T during which the orientation return occurred was 4 seconds. .
(比較例3)
ラミネート速度を150mpm、ラミネート前の金属板の加熱温度を265℃、ラミネートロールの表面温度を80℃、及び配向復帰が生じる時間Tを1秒とした以外は、実施例6と同様にして行った。 (Comparative Example 3)
The procedure was performed in the same manner as in Example 6, except that the laminating speed was 150 mpm, the heating temperature of the metal plate before laminating was 265 ° C., the surface temperature of the laminating roll was 80 ° C., and the time T during which the orientation return occurred was 1 second. .
ラミネート速度を150mpm、ラミネート前の金属板の加熱温度を265℃、ラミネートロールの表面温度を80℃、及び配向復帰が生じる時間Tを1秒とした以外は、実施例6と同様にして行った。 (Comparative Example 3)
The procedure was performed in the same manner as in Example 6, except that the laminating speed was 150 mpm, the heating temperature of the metal plate before laminating was 265 ° C., the surface temperature of the laminating roll was 80 ° C., and the time T during which the orientation return occurred was 1 second. .
(比較例4)
ポリブチレンテレフタレート層Aとして、未延伸の二層フィルムを準備した。二層フィルムのうち表層は、イソフタル酸が11モル%共重合されたポリエチレンテレフタレート/イソフタレート樹脂、下層はポリブチレンテレフタレートのホモポリマー樹脂とした。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び配向復帰が生じる時間Tは、各々表1に示すものとした。それ以外は実施例1と同様にして行った。 (Comparative Example 4)
An unstretched two-layer film was prepared as the polybutylene terephthalate layer A. The surface layer of the two-layer film was a polyethylene terephthalate / isophthalate resin in which isophthalic acid was copolymerized at 11 mol%, and the lower layer was a polybutylene terephthalate homopolymer resin.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1. Other than that, it carried out similarly to Example 1.
ポリブチレンテレフタレート層Aとして、未延伸の二層フィルムを準備した。二層フィルムのうち表層は、イソフタル酸が11モル%共重合されたポリエチレンテレフタレート/イソフタレート樹脂、下層はポリブチレンテレフタレートのホモポリマー樹脂とした。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び配向復帰が生じる時間Tは、各々表1に示すものとした。それ以外は実施例1と同様にして行った。 (Comparative Example 4)
An unstretched two-layer film was prepared as the polybutylene terephthalate layer A. The surface layer of the two-layer film was a polyethylene terephthalate / isophthalate resin in which isophthalic acid was copolymerized at 11 mol%, and the lower layer was a polybutylene terephthalate homopolymer resin.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1. Other than that, it carried out similarly to Example 1.
(比較例5)
ポリブチレンテレフタレート層Aとして、未延伸の二層フィルムを準備した。二層フィルムのうち表層は、ポリエチレンテレフタレートのホモポリマー、下層はポリブチレンテレフタレートのホモポリマーとした。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び配向復帰が生じる時間Tは、各々表1に示すものとした。それ以外は実施例1と同様にして行った。 (Comparative Example 5)
An unstretched two-layer film was prepared as the polybutylene terephthalate layer A. The surface layer of the two-layer film was a homopolymer of polyethylene terephthalate, and the lower layer was a homopolymer of polybutylene terephthalate.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1. Other than that, it carried out similarly to Example 1.
ポリブチレンテレフタレート層Aとして、未延伸の二層フィルムを準備した。二層フィルムのうち表層は、ポリエチレンテレフタレートのホモポリマー、下層はポリブチレンテレフタレートのホモポリマーとした。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び配向復帰が生じる時間Tは、各々表1に示すものとした。それ以外は実施例1と同様にして行った。 (Comparative Example 5)
An unstretched two-layer film was prepared as the polybutylene terephthalate layer A. The surface layer of the two-layer film was a homopolymer of polyethylene terephthalate, and the lower layer was a homopolymer of polybutylene terephthalate.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation was restored were as shown in Table 1. Other than that, it carried out similarly to Example 1.
(実施例7)
金属板の片面には実施例1と同様のポリブチレンテレフタレートのホモポリマーからなる二軸延伸フィルムを積層した。一方で、金属板の他方の面には、ポリエチレンテレフタレートのホモポリマーの二軸延伸フィルム、厚み12μmを配向結晶が残る条件にて積層した。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tは、各々表2に示すものとした。それ以外は、実施例1と同様にして行った。 (Example 7)
On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, on the other surface of the metal plate, a biaxially stretched film of a homopolymer of polyethylene terephthalate and a thickness of 12 μm were laminated under the condition that oriented crystals remain.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 1.
金属板の片面には実施例1と同様のポリブチレンテレフタレートのホモポリマーからなる二軸延伸フィルムを積層した。一方で、金属板の他方の面には、ポリエチレンテレフタレートのホモポリマーの二軸延伸フィルム、厚み12μmを配向結晶が残る条件にて積層した。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tは、各々表2に示すものとした。それ以外は、実施例1と同様にして行った。 (Example 7)
On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, on the other surface of the metal plate, a biaxially stretched film of a homopolymer of polyethylene terephthalate and a thickness of 12 μm were laminated under the condition that oriented crystals remain.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 1.
(実施例8)
金属板の片面には実施例1と同様のポリブチレンテレフタレートのホモポリマーからなる二軸延伸フィルムを積層した。一方で、金属板の他方の面には、イソフタル酸が11モル%共重合されたポリエチレンテレフタレート/イソフタレート樹脂の二軸延伸フィルム、厚み19μmを配向結晶が残らない条件にて積層した。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tは、各々表2に示すものとした。それ以外は、実施例2と同様にして行った。 (Example 8)
On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, a biaxially stretched film of a polyethylene terephthalate / isophthalate resin in which isophthalic acid was copolymerized at 11 mol% and a thickness of 19 μm were laminated on the other surface of the metal plate under the condition that no oriented crystals remain.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 2.
金属板の片面には実施例1と同様のポリブチレンテレフタレートのホモポリマーからなる二軸延伸フィルムを積層した。一方で、金属板の他方の面には、イソフタル酸が11モル%共重合されたポリエチレンテレフタレート/イソフタレート樹脂の二軸延伸フィルム、厚み19μmを配向結晶が残らない条件にて積層した。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tは、各々表2に示すものとした。それ以外は、実施例2と同様にして行った。 (Example 8)
On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, a biaxially stretched film of a polyethylene terephthalate / isophthalate resin in which isophthalic acid was copolymerized at 11 mol% and a thickness of 19 μm were laminated on the other surface of the metal plate under the condition that no oriented crystals remain.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 2.
(実施例9)
金属板の片面には実施例1と同様のポリブチレンテレフタレートのホモポリマーからなる二軸延伸フィルムを積層した。一方で、金属板の他方の面には、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のブレンド樹脂(ブレンド比4:6)からなる二軸延伸フィルム、厚み18μmを配向結晶が残らない条件にて積層した。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tは、各々表2に示すものとした。それ以外は、実施例3と同様にして行った。 (Example 9)
On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, on the other surface of the metal plate, a biaxially stretched film made of a blend resin of polyethylene terephthalate and polybutylene terephthalate (blend ratio 4: 6) and a thickness of 18 μm were laminated under the condition that no oriented crystals remain.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 3.
金属板の片面には実施例1と同様のポリブチレンテレフタレートのホモポリマーからなる二軸延伸フィルムを積層した。一方で、金属板の他方の面には、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のブレンド樹脂(ブレンド比4:6)からなる二軸延伸フィルム、厚み18μmを配向結晶が残らない条件にて積層した。
ラミネート前の金属板の加熱温度、ラミネートロールの表面温度、ラミネート速度、及び、配向復帰が生じる時間Tは、各々表2に示すものとした。それ以外は、実施例3と同様にして行った。 (Example 9)
On one side of the metal plate, a biaxially stretched film made of the same homopolymer of polybutylene terephthalate as in Example 1 was laminated. On the other hand, on the other surface of the metal plate, a biaxially stretched film made of a blend resin of polyethylene terephthalate and polybutylene terephthalate (blend ratio 4: 6) and a thickness of 18 μm were laminated under the condition that no oriented crystals remain.
The heating temperature of the metal plate before the lamination, the surface temperature of the laminating roll, the laminating speed, and the time T during which the orientation return occurs were as shown in Table 2. Other than that, it carried out similarly to Example 3.
実施例1~6によれば、本実施形態によるポリエステル樹脂被覆金属板は、耐衝撃性、成形性、レトルト密着性、レトルトブラッシング耐性のすべての項目において優れた結果となった。
According to Examples 1 to 6, the polyester resin-coated metal sheet according to the present embodiment exhibited excellent results in all items of impact resistance, moldability, retort adhesion, and retort brushing resistance.
一方で、比較例1~3によれば、ポリブチレンテレフタレート層AのX線回折強度比Rの値が1.3以上6.6以下でない場合、耐衝撃性、成形性、レトルト密着性、レトルトブラッシング耐性のいずれか又は複数の項目で好ましくない結果となった。
On the other hand, according to Comparative Examples 1 to 3, when the value of the X-ray diffraction intensity ratio R of the polybutylene terephthalate layer A is not more than 1.3 and not more than 6.6, the impact resistance, the moldability, the retort adhesion, the retort Unsatisfactory results were obtained in one or more items of the brushing resistance.
また、比較例4~5によれば、ポリブチレンテレフタレート層Aを複層樹脂とした場合、金属板に接する層をポリブチレンテレフタレートのホモポリマーとしても、表層の樹脂の結晶化速度が遅い場合には、レトルトブラッシング(白斑)が発生する結果となった。
Further, according to Comparative Examples 4 and 5, when the polybutylene terephthalate layer A is a multilayer resin, even when the layer in contact with the metal plate is a homopolymer of polybutylene terephthalate, when the crystallization rate of the resin in the surface layer is low, Resulted in retort brushing (white spots).
実施例7~9によれば、金属板の片面にポリブチレンテレフタレート層Aを積層し、他方にそれ以外のポリエステル樹脂を積層した場合、ラミネート条件をポリブチレンテレフタレート層Aの形成に合わせた条件としても、反対面の樹脂層が良好に形成され、容器又は容器蓋として実用可能な結果となった。
According to Examples 7 to 9, when the polybutylene terephthalate layer A is laminated on one side of the metal plate and another polyester resin is laminated on the other side, the laminating conditions are set in accordance with the formation of the polybutylene terephthalate layer A. Also, the resin layer on the opposite surface was formed well, and the result was practically usable as a container or a container lid.
なお、上記した実施例において、耐衝撃性評価、成形性評価、レトルト密着性評価、及びレトルトブラッシング評価については、容器により評価を行っている。一般的に容器蓋は、容器よりも加工度が低いといえるため、本発明の特徴であるX線回折強度比Rの値が規定の範囲内であれば、容器蓋についても、耐衝撃性評価、成形性評価、レトルト密着性評価、及びレトルトブラッシング評価のいずれも良好な結果となることは明らかといえる。
In the examples described above, the impact resistance evaluation, the moldability evaluation, the retort adhesion evaluation, and the retort brushing evaluation were evaluated using containers. Generally, it can be said that the container lid has a lower degree of processing than the container. Therefore, if the value of the X-ray diffraction intensity ratio R, which is a feature of the present invention, is within the specified range, the container lid is also evaluated for impact resistance. It can be clearly seen that all of the evaluations of moldability, evaluation of retort adhesion, and evaluation of retort brushing give good results.
本発明によれば、飲料缶や食品缶等の容器や容器蓋において、レトルトブラッシング(白斑)の発生を抑制できる。また、耐衝撃性、成形性、レトルト密着性、等に優れるポリエステル樹脂被覆金属板を提供することができ、産業上の利用可能性が極めて高い。
According to the present invention, occurrence of retort brushing (white spots) can be suppressed in a container such as a beverage can or a food can or a container lid. Further, it is possible to provide a polyester resin-coated metal plate excellent in impact resistance, moldability, retort adhesion, and the like, and has extremely high industrial applicability.
Claims (9)
- 金属板と、
前記金属板の少なくとも片面に接するように積層されたポリブチレンテレフタレート層と、を有し、
前記ポリブチレンテレフタレート層における(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内であることを特徴とするポリエステル樹脂被覆金属板。
(ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。) A metal plate,
Having a polybutylene terephthalate layer laminated so as to be in contact with at least one surface of the metal plate,
A polyester resin, wherein the ratio (R) of the X-ray diffraction intensity of the (100) plane and the X-ray diffraction intensity of the (1-11) plane in the polybutylene terephthalate layer is in the range of 1.3 to 6.6. Coated metal plate.
(However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.) - 前記ポリブチレンテレフタレート層は、前記金属板の片面に積層されており、
前記金属板の他方の面には前記ポリブチレンテレフタレート層とは異なるポリエステル樹脂層が積層されている、請求項1に記載のポリエステル樹脂被覆金属板。 The polybutylene terephthalate layer is laminated on one surface of the metal plate,
The polyester resin-coated metal plate according to claim 1, wherein a polyester resin layer different from the polybutylene terephthalate layer is laminated on the other surface of the metal plate. - 前記異なるポリエステル樹脂層は、ポリエチレンテレフタレート樹脂層、イソフタル酸が共重合されたポリエチレンテレフタレート樹脂層、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がブレンドされた樹脂層、および、イソフタル酸が共重合された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とがブレンドされた樹脂層の中から選択されるいずれかである請求項2に記載のポリエステル樹脂被覆金属板。 The different polyester resin layer is a polyethylene terephthalate resin layer, a polyethylene terephthalate resin layer in which isophthalic acid is copolymerized, a resin layer in which polyethylene terephthalate and polybutylene terephthalate are blended, and a polyethylene terephthalate and polybutylene in which isophthalic acid is copolymerized. The polyester resin-coated metal plate according to claim 2, which is any one selected from a resin layer blended with butylene terephthalate.
- 前記異なるポリエステル樹脂層は、未配向の状態でラミネートされている請求項2又は3に記載のポリエステル樹脂被覆金属板。 The polyester resin-coated metal plate according to claim 2, wherein the different polyester resin layers are laminated in a non-oriented state.
- 前記X線回折強度比Rが、1.3以上3.0以下の範囲内である請求項1~4に記載のポリエステル樹脂被覆金属板。 (5) The polyester resin-coated metal plate according to any one of (1) to (4), wherein the X-ray diffraction intensity ratio R is in the range of 1.3 or more and 3.0 or less.
- 前記X線回折強度比Rが、1.3以上2.7以下の範囲内である請求項5に記載のポリエステル樹脂被覆金属板。 The polyester resin-coated metal sheet according to claim 5, wherein the X-ray diffraction intensity ratio R is in the range of 1.3 or more and 2.7 or less.
- 請求項1~6のいずれか一項に記載のポリエステル樹脂被覆金属板を用いて成形された容器。 (7) A container molded using the polyester resin-coated metal plate according to any one of (1) to (6).
- 請求項1~6のいずれか一項に記載のポリエステル樹脂被覆金属板を用いて成形された容器蓋。 (7) A container lid formed using the polyester resin-coated metal plate according to any one of (1) to (6).
- 金属板の少なくとも片面に対し、積層後のポリブチレンテレフタレート層における(100)面のX線回折強度と(1-11)面のX線回折強度比Rが1.3以上6.6以下の範囲内となるようにラミネートロールを用いて二軸延伸ポリブチレンテレフタレートフィルムを積層するポリエステル樹脂被覆金属板の製造方法であって、
前記金属板の板温を240℃~300℃の範囲内とし、前記ラミネートロールの表面温度を30℃~180℃の範囲内としつつ、かつ、ラミネート前の金属板の板温とラミネートロールの表面温度との温度差を80℃以上確保した条件にて前記二軸延伸ポリブチレンテレフタレートフィルムを前記金属板に積層する積層工程と、
前記積層工程の後で、前記積層工程により溶解した前記二軸延伸ポリブチレンテレフタレートフィルムの配向結晶が復帰する配向復帰工程と、
前記配向復帰工程の後で、前記二軸延伸ポリブチレンテレフタレートフィルムが積層された金属板を急冷する急冷工程と、
を含むことを特徴とするポリエステル樹脂被覆金属板の製造方法。
(ただし、前記(100)面のX線回折強度は回折角2θが23.0°~24.0°の範囲に確認される最大値であり、前記(1-11)面のX線回折強度は回折角2θが25.0°~26.0°の範囲に確認される最大値であり、前記X線回折強度比R=(100)面の回折強度/(1-11)面の回折強度である。) The ratio R of the X-ray diffraction intensity of the (100) plane and the X-ray diffraction intensity of the (1-11) plane of the laminated polybutylene terephthalate layer to at least one side of the metal plate is in a range of 1.3 to 6.6. A method for producing a polyester resin-coated metal plate by laminating a biaxially stretched polybutylene terephthalate film using a laminating roll to be inside,
The temperature of the metal plate is set within the range of 240 ° C. to 300 ° C., the surface temperature of the laminating roll is set within the range of 30 ° C. to 180 ° C. A laminating step of laminating the biaxially stretched polybutylene terephthalate film on the metal plate under the condition that the temperature difference from the temperature is maintained at 80 ° C. or higher,
After the laminating step, an orientation returning step in which the oriented crystals of the biaxially stretched polybutylene terephthalate film dissolved in the laminating step return,
After the orientation return step, a quenching step of quenching the metal plate on which the biaxially stretched polybutylene terephthalate film is laminated,
A method for producing a polyester resin-coated metal sheet, comprising:
(However, the X-ray diffraction intensity of the (100) plane is the maximum value at which the diffraction angle 2θ is confirmed in the range of 23.0 ° to 24.0 °, and the X-ray diffraction intensity of the (1-11) plane is Is the maximum value at which the diffraction angle 2θ is in the range of 25.0 ° to 26.0 °, and the X-ray diffraction intensity ratio R = (100) plane diffraction intensity / (1-11) plane diffraction intensity Is.)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-142939 | 2018-07-30 | ||
JP2018142939A JP7080125B2 (en) | 2018-07-30 | 2018-07-30 | Manufacturing method of polyester resin-coated metal plate, polyester resin-coated metal plate, container and container lid made of the polyester resin-coated metal plate. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020026803A1 true WO2020026803A1 (en) | 2020-02-06 |
Family
ID=69231637
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/028039 WO2020026803A1 (en) | 2018-07-30 | 2019-07-17 | Polyester-resin-coated metal sheet, method for producing polyester-resin-coated metal sheet, and container and container lid that comprise polyester-resin-coated metal sheet |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP7080125B2 (en) |
WO (1) | WO2020026803A1 (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5149389A (en) * | 1987-10-15 | 1992-09-22 | Cmb Foodcan Plc | Laminated metal sheet |
JP2003081241A (en) * | 2001-09-14 | 2003-03-19 | Daiwa Can Co Ltd | Drawn-formed can made of aluminum and its manufacturing method |
JP2006326902A (en) * | 2005-05-24 | 2006-12-07 | Nippon Steel Corp | Composite-layered polyester film laminated metal sheet for container and its manufacturing method |
JP2007090667A (en) * | 2005-09-29 | 2007-04-12 | Toyo Kohan Co Ltd | Method for manufacturing metal plate covered with organic resin and apparatus for manufacturing metal plate covered with organic resin |
JP2015134875A (en) * | 2014-01-17 | 2015-07-27 | 東洋鋼鈑株式会社 | Resin film for metal plate laminate, resin laminate metal plate, container and container lid using the same |
WO2016159260A1 (en) * | 2015-03-31 | 2016-10-06 | Jfeスチール株式会社 | Laminate metal plate for container |
WO2019167417A1 (en) * | 2018-03-01 | 2019-09-06 | 東洋鋼鈑株式会社 | Resin-coated metal sheet for container, container formed of resin-coated metal sheet, and method for manufacturing resin-coated metal sheet |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5863393B2 (en) | 2011-11-02 | 2016-02-16 | 興人フィルム&ケミカルズ株式会社 | Laminated metal sheet for cans containing biaxially stretched polybutylene terephthalate film |
-
2018
- 2018-07-30 JP JP2018142939A patent/JP7080125B2/en active Active
-
2019
- 2019-07-17 WO PCT/JP2019/028039 patent/WO2020026803A1/en active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5149389A (en) * | 1987-10-15 | 1992-09-22 | Cmb Foodcan Plc | Laminated metal sheet |
JP2003081241A (en) * | 2001-09-14 | 2003-03-19 | Daiwa Can Co Ltd | Drawn-formed can made of aluminum and its manufacturing method |
JP2006326902A (en) * | 2005-05-24 | 2006-12-07 | Nippon Steel Corp | Composite-layered polyester film laminated metal sheet for container and its manufacturing method |
JP2007090667A (en) * | 2005-09-29 | 2007-04-12 | Toyo Kohan Co Ltd | Method for manufacturing metal plate covered with organic resin and apparatus for manufacturing metal plate covered with organic resin |
JP2015134875A (en) * | 2014-01-17 | 2015-07-27 | 東洋鋼鈑株式会社 | Resin film for metal plate laminate, resin laminate metal plate, container and container lid using the same |
WO2016159260A1 (en) * | 2015-03-31 | 2016-10-06 | Jfeスチール株式会社 | Laminate metal plate for container |
WO2019167417A1 (en) * | 2018-03-01 | 2019-09-06 | 東洋鋼鈑株式会社 | Resin-coated metal sheet for container, container formed of resin-coated metal sheet, and method for manufacturing resin-coated metal sheet |
Also Published As
Publication number | Publication date |
---|---|
JP2020019166A (en) | 2020-02-06 |
JP7080125B2 (en) | 2022-06-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5673860B2 (en) | Laminated metal plate and canned food containers | |
JP5403195B1 (en) | Laminated metal plate and canned food containers | |
JP6028886B1 (en) | Resin-coated metal plate for containers | |
US10399303B2 (en) | Resin-coated metal sheet for can lids | |
JP2014166856A (en) | Laminate metal plate for 2-piece can and 2-piece laminate can body | |
JP4806933B2 (en) | Polyester resin laminated metal container | |
JP5082269B2 (en) | Resin-coated metal plate for containers | |
JP2018140542A (en) | Can lid for canned food | |
WO2020026803A1 (en) | Polyester-resin-coated metal sheet, method for producing polyester-resin-coated metal sheet, and container and container lid that comprise polyester-resin-coated metal sheet | |
JP5920279B2 (en) | LAMINATED METAL PLATE, METHOD FOR PRODUCING LAMINATED METAL PLATE, AND FOOD CANNED CONTAINER | |
JP2007253453A (en) | Resin coated metal sheet for container | |
JP6565957B2 (en) | Resin-coated metal plate for can lids | |
CN108367542B (en) | Laminated steel sheet for double-sided resin-coated container | |
US20210031999A1 (en) | Resin-coated metal sheet for container, container formed of resin-coated metal sheet, and method for manufacturing resin-coated metal sheet | |
JP2803837B2 (en) | Manufacturing method of polyester resin film laminated steel sheet | |
JPH1024521A (en) | Thermoplastic-resin-coated metal plate having good molding workability and impact resistant workability, and its manufacture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19844679 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19844679 Country of ref document: EP Kind code of ref document: A1 |