WO2016143817A1 - 金属板ラミネート用ポリエステル系フィルム - Google Patents
金属板ラミネート用ポリエステル系フィルム Download PDFInfo
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- WO2016143817A1 WO2016143817A1 PCT/JP2016/057358 JP2016057358W WO2016143817A1 WO 2016143817 A1 WO2016143817 A1 WO 2016143817A1 JP 2016057358 W JP2016057358 W JP 2016057358W WO 2016143817 A1 WO2016143817 A1 WO 2016143817A1
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- film
- polyester
- layer
- resin
- metal plate
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/34—Coverings or external coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/66—Cans, tins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- the present invention relates to a polyester-based film for laminating metal plates, and in particular, in a three-piece can, it is affixed to the inner surface of a can for the purpose of preventing corrosion of metal containers for beverages and beverages such as soft drinks, coffee, and canned foods.
- the present invention relates to a polyester-based film for laminating metal plates used for bonding.
- a paint is generally applied to prevent corrosion of the inner and outer surfaces of a metal can, and a thermosetting resin is used as the paint.
- thermosetting resin in general, after applying a paint in which a thermosetting resin is dissolved in a solvent to the surface of the metal can, a temperature of 190 ° C. or higher for several minutes is required. Since heating is necessary and a large amount of organic solvent is scattered during baking, improvements such as simplification of the process and prevention of pollution are desired.
- thermoplastic resin film As a means for solving the above problems. For example, by applying a thermosetting adhesive in advance to a polyolefin film such as a polyester film or a polypropylene film, and then pasting it on a metal plate, the additives contained in the paint and the incomplete crosslinking reaction This is a method for suppressing the adverse effects of the low molecular weight substances resulting from the above to the contents of the metal can.
- thermoplastic resin film when a polyolefin film such as polypropylene is used as the thermoplastic resin film, it is possible to simplify the work environment problem and the process, but the low molecular weight substance from the inner surface side of the metal can to the contents Migration cannot be suppressed sufficiently. Moreover, since such a film is inferior in heat resistance, the thermoplastic resin film affixed to the metal plate peels off when it receives a heat history in the can making process or a heat history such as a retort treatment after the can making. Sometimes.
- Patent Documents 1, 2, 3, and 4 a polyester-based laminated film having an upper layer made of a polyester-based resin and a lower layer made of a polyester-based resin having an adhesive function is laminated on a metal plate.
- a method is described. When this method is used, work environment problems and simplification of the process can be achieved, and problems regarding heat resistance of the polyolefin film can be improved.
- the polyester film may shrink or peel off from the metal plate due to heat treatment for improving the finish of the can during can manufacturing, heat treatment for repairing the joint part of the can using a band-shaped film, etc. There is. This is because the lower melting point is lower than the heat treatment temperature.
- Patent Document 5 when a polyethylene terephthalate resin and a polybutylene terephthalate resin are used in combination, the contents are filled after the can is made and corroded on the inner surface of the metal can when stored for a long period of time. There is a problem that is likely to occur.
- Patent Document 6 when a low-melting-point component is used in combination with a layer on the side opposite to the surface to be bonded to the metal plate, that is, the surface on the side in contact with the so-called food or drink, the film is formed at high speed.
- the polyester block copolymer used in combination as a low melting point component is incompatible with the polyester resin and has a low melting point of 180 to 200 ° C.
- the present invention has been made in view of the above circumstances, and its purpose is to have corrosion resistance, can be bonded to a metal plate at a relatively low temperature, has excellent can-making properties, and after can-making. It is an object of the present invention to provide a polyester film for laminating metal plates, which can easily repair the joint portion. Another object of the present invention is to provide a film laminated metal plate obtained by laminating the polyester film on a metal plate and a metal container formed by molding the film laminated metal plate.
- the polyester film for laminating a metal plate according to the present invention is a polyester film composed of two layers of an A layer and a B layer, and the resin constituting the A layer is in 100 mol% of all the structural units of polyester,
- the polyester resin having a total content of ethylene terephthalate units and diethylene terephthalate units of 95 mol% or more and 98 mol% or less, and the resin constituting the B layer is a polyester resin (B1) 80 ⁇ 100% by mass and 0 to 20% by mass of a polyester resin (B2) having a composition different from that of the polyester resin (B1).
- the resin constituting the A layer is preferably 2 mol% or more and 5 mol% or less of ethylene isophthalate units in 100 mol% of all the structural units of polyester.
- the thickness ratio of the A layer and the B layer is preferably 75:25 to 95: 5, and the laminating temperature between the B layer and the metal plate is preferably 200 ° C. or less.
- the polyester-based resin (B1) preferably contains 5 to 15 mol% of ethylene isophthalate units in 100 mol% of all the structural units of polyester. Moreover, it is preferable that the said polyester-type resin (B1) consists of a polyethylene terephthalate and a polyethylene isophthalate.
- the polyester-based resin (B2) is preferably polybutylene terephthalate.
- the present invention also includes a film-laminated metal plate in which the B layer of the polyester film is laminated on at least one surface of the metal plate. Furthermore, the present invention also includes a metal container formed by forming the film-laminated metal plate.
- the polyester-based film of the present invention has excellent corrosion resistance and can be bonded to a metal plate at a lower temperature than before. Moreover, when the polyester-type film of this invention is used, it can be made at high speed and it is suitable also for repair of a junction part. Even if heat treatment is performed to improve the finish of the can during can manufacturing, or heat treatment is performed to repair the joint of the can, the film may shrink or the film may peel off from the metal plate. Therefore, it is suitable for use as a film for metal containers for storing beverages and food products.
- the polyester film for laminating a metal plate of the present invention is a polyester film composed of two layers of an A layer and a B layer.
- the A layer is a layer having heat resistance in the can-making process
- the B layer is a layer having laminate adhesion by thermocompression bonding in addition to the same heat resistance as the A layer.
- a layer becomes a layer which contacts the contents, such as foodstuff, or the surface of a container
- B layer is metal It is preferable to laminate on the plate side.
- the A layer is formed from a composition containing a polyester resin mainly composed of ethylene terephthalate.
- the resin constituting the A layer is a polyester resin in which the total content of ethylene terephthalate units and diethylene terephthalate units is 95 mol% or more and 98 mol% or less in 100 mol% of all the structural units of polyester. .
- the heat resistance may be inferior.
- the film is subjected to high-temperature heat treatment during can making, troubles such as shrinkage and peeling may occur.
- a structural unit of polyester only one of the ethylene terephthalate unit or the diethylene terephthalate unit may be included.
- the composition forming the polyester resin of the A layer contains a polyvalent carboxylic acid component other than terephthalic acid and a polyhydric alcohol component other than ethylene glycol and diethylene glycol. That is, the resin constituting the A layer includes a unit derived from a polyvalent carboxylic acid other than terephthalic acid and a unit derived from a polyhydric alcohol other than ethylene glycol and diethylene glycol.
- polyvalent carboxylic acids other than terephthalic acid examples include aromatic polyvalent carboxylic acids such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid; adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid And aliphatic dicarboxylic acids such as acids and dimer acids; alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid; and the like.
- polyhydric alcohols other than ethylene glycol and diethylene glycol include aliphatic polyhydric alcohols such as triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, dodecamethylene glycol, and neopentyl glycol; cyclohexanedimethanol, cyclohexane Alicyclic diols such as diethanol; aliphatic polyhydric alcohols such as trimethylolpropane and pentaerythritol; aromatic polyhydric alcohols such as ethylene oxide adducts of bisphenol derivatives; and the like.
- aliphatic polyhydric alcohols such as triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, dodecamethylene glycol, and neopentyl glycol
- cyclohexanedimethanol cyclohex
- the polyhydric alcohols other than ethylene glycol and diethylene glycol that form the polyester resin of the A layer have a structurally long straight chain portion and easily pass an ionic component. Therefore, from the viewpoint of corrosion resistance, the resin constituting the A layer is 2 to 5 mol% of the units other than the ethylene terephthalate unit and diethylene terephthalate unit in 100 mol% of all the structural units of polyester, preferably 2 to 3 mol%.
- the units other than the ethylene terephthalate unit and the diethylene terephthalate unit preferably include an ethylene isophthalate unit, and more preferably includes only an ethylene isophthalate unit.
- the unit constituting the A layer is composed of an ethylene terephthalate unit and an ethylene isophthalate unit, that is, the resin constituting the A layer is preferably composed of polyethylene terephthalate and polyethylene isophthalate.
- the unit derived from diethylene glycol generated as a by-product during polymerization is preferably 5 mol% or less, more preferably 3 mol% or less, in 100 mol% of all structural units of the polyester. .
- polyester resin one type of polyester polymer may be used alone, or a mixture of a plurality of polyester polymers may be used.
- various additives such as lubricant particles and antioxidants may be contained in a proportion of 5% by mass or less in 100% by mass of the composition containing the polyester resin.
- the intrinsic viscosity of the resin constituting the layer A is preferably 0.5 to 0.7 dl / g, more preferably 0.55 to 0.67 dl / g, still more preferably 0.57 to 0.65 dl / g, and particularly preferably Is 0.58 to 0.60 dl / g.
- the intrinsic viscosity is less than 0.5 dl / g, the film forming operability is very poor, and even if the film can be formed, a thermally deteriorated product derived from a low molecular weight material is generated and used as a polyester film for metal plate lamination. Can be difficult.
- the resin when the intrinsic viscosity exceeds 0.7 dl / g, the resin is melted in the film forming process, and excessive heat and pressure are applied when the resin is extruded by the extruder, resulting in thermal decomposition in the extruder. Since the amount of low molecular weight increases or the load of extrusion is too great, it is difficult to extrude a uniform amount of resin from the extruder, and it may be difficult to obtain a polyester film for laminating metal plates with good quality There is.
- the B layer is formed from a composition containing a polyester resin mainly composed of ethylene terephthalate.
- the resin constituting the B layer is a polyester resin mainly composed of ethylene terephthalate (hereinafter referred to as resin B1) 80 to 100% by mass, and a polyester resin (hereinafter referred to as resin B2) 0 having a composition different from that of resin B1. It consists of ⁇ 20% by mass.
- the B layer is a polyester-based resin composed of 85 to 95% by mass of the resin B1 and 5 to 15% by mass of the resin B2.
- the resin B1 “mainly composed of ethylene terephthalate” means that the ethylene terephthalate unit is 80 mol% or more in 100 mol% of all constituent units of polyester.
- all the structural units of polyester are composed of an ethylene terephthalate unit and an ethylene isophthalate unit, that is, the resin B1 is preferably composed of polyethylene terephthalate and polyethylene isophthalate.
- Resin B1 may contain a unit derived from a polyhydric alcohol other than ethylene glycol and / or a unit derived from a polyvalent carboxylic acid other than terephthalic acid.
- Units derived from polyhydric alcohols other than ethylene glycol are ester units composed of polyhydric alcohols other than ethylene glycol and terephthalic acid.
- Units derived from polyvalent carboxylic acids other than terephthalic acid are units other than terephthalic acid. This means an ester unit composed of a monovalent carboxylic acid and ethylene glycol.
- polyvalent carboxylic acids other than terephthalic acid examples include aromatic polyvalent carboxylic acids such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid; adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid And aliphatic dicarboxylic acids such as acids and dimer acids; alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid; and the like.
- polyhydric alcohols other than ethylene glycol examples include aliphatic polyhydric alcohols such as diethylene glycol, triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, dodecamethylene glycol, and neopentyl glycol; cyclohexanedimethanol, cyclohexane Alicyclic diols such as diethanol; aliphatic polyhydric alcohols such as trimethylolpropane and pentaerythritol; aromatic polyhydric alcohols such as ethylene oxide adducts of bisphenol derivatives; and the like.
- aliphatic polyhydric alcohols such as diethylene glycol, triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, dodecamethylene glycol, and neopentyl glycol
- Resin B1 has an ethylene isophthalate unit of preferably 0 mol% or more and 20 mol% or less, preferably 5 mol% or more and 15 mol% or less, in 100 mol% of all structural units of polyester.
- the resin B2 “having a composition different from that of the polyester-based resin mainly composed of ethylene terephthalate” means that the ethylene terephthalate unit is less than 20 mol% in 100 mol% of all the structural units of the polyester.
- Resin B2 contains a unit derived from a polyhydric alcohol other than ethylene glycol and / or a unit derived from a polyvalent carboxylic acid other than terephthalic acid.
- polyvalent carboxylic acids other than terephthalic acid and polyhydric alcohols other than ethylene glycol are the same as those for resin B1.
- Resin B2 is preferably 80 mol% or more of butylene terephthalate units in 100 mol% of all structural units of polyester, more preferably 100 mol% (resin B2 is polybutylene terephthalate).
- various additives such as lubricant particles and antioxidants may be contained in a proportion of 5% by mass or less in 100% by mass of the composition containing the polyester resin.
- the resin having the above-described structure is used as the resin constituting the B layer, the fluidity of the B layer does not increase greatly even when heated in a can manufacturing process or the like, and the dimensional change of the A layer is difficult to increase.
- resin of said structure is used as resin which comprises B layer, B layer will become easy to closely_contact
- the melting point of the resin constituting the B layer is preferably 220 to 235 ° C., more preferably 225 to 235 ° C., and further preferably 225 to 233 ° C. If the melting point of the resin constituting the B layer is less than 220 ° C., the fluidity of the B layer increases due to the thermal history in the can manufacturing process or the like, and the dimensional change of the A layer may increase. On the other hand, when the melting point of the resin constituting the B layer exceeds 235 ° C., it becomes close to the melting point of the A layer, so that excessive heat may be given to the A layer when it is attempted to ensure adhesion to the metal plate by heat fusion. There is.
- the intrinsic viscosity of the resin constituting the B layer is preferably 0.5 to 0.7 dl / g, more preferably 0.55 to 0.65 dl / g.
- the film forming operability is very poor, and even if the film can be formed, a thermally deteriorated product derived from a low molecular weight material is generated and used as a polyester film for metal plate lamination. Can be difficult.
- the resin when the intrinsic viscosity exceeds 0.7 dl / g, the resin is melted in the film forming process, and excessive heat and pressure are applied when the resin is extruded by the extruder, resulting in thermal decomposition in the extruder. Since the amount of low molecular weight increases or the load of extrusion is too great, it is difficult to extrude a uniform amount of resin from the extruder, and it may be difficult to obtain a polyester film for laminating metal plates with good quality There is.
- the temperature capable of laminating the B layer and the metal plate is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 160 ° C. or lower.
- the difference in glass transition temperature (Tg) between the resin constituting the A layer and the resin constituting the B layer is 10 ° C. or less. It is preferable that it is, and it is more preferable that it is 6 degrees C or less. If the difference in Tg exceeds 10 ° C., the produced film is likely to curl and the handleability deteriorates, which is not preferable.
- the total thickness of the polyester film of the present invention (the total thickness of the A layer and the B layer) is usually preferably 9 ⁇ m or more and 25 ⁇ m or less, and more preferably 10 ⁇ m or more and 15 ⁇ m or less. If the total thickness is less than 9 ⁇ m, the gas barrier properties are inferior, the corrosion resistance is deteriorated, and further, low molecular weight substances from metal containers may penetrate into beverages and foodstuffs. On the other hand, even if the total thickness of the film exceeds 25 ⁇ m, the corresponding improvement effect cannot be obtained, which is disadvantageous in terms of manufacturing cost.
- the A layer of the polyester film in the present invention becomes the outer surface of the film laminated metal plate when forming the film laminated metal plate, the film is damaged in the can making step or the like, or the can is made by scraping the film. It can function to prevent contamination of the can manufacturing apparatus.
- the dynamic friction coefficient at 80 ° C. of the polyester film surface is preferably 0.45 or less, more preferably 0.43 or less, and further preferably 0.40 or less. .
- the dynamic friction coefficient on the surface of the polyester film is 0.45 or less, damage to the film in the can making process or the like, and contamination of the can making apparatus in the can making process due to the film being scraped can be prevented.
- Examples of the method for reducing the coefficient of dynamic friction on the surface of the layer A of the polyester film for metal plate lamination of the present invention to 0.45 or less include, for example, a method of containing fine particles described later in the film, and forming fine spherulites of the polyester resin. And a method of incorporating fine particles into the film is preferable.
- a method of incorporating fine particles into the film is preferable.
- the fine particles are not particularly limited as long as they are insoluble in polyester and inert, and examples thereof include amorphous inorganic particles and crosslinked polymer particles. Further, in order to adjust the particle size and particle size distribution of the fine particles, pulverization, classification, or the like may be performed.
- materials for forming amorphous inorganic particles include metal oxides such as silica, alumina, zirconia, and titanium oxide; complex oxides such as kaolin, zeolite, sericite, and sepiolite; sulfates such as calcium sulfate and barium sulfate; calcium phosphate And phosphates such as zirconium phosphate; carbonates such as calcium carbonate, and the like.
- these inorganic fine particles may be natural products or synthetic products.
- the crosslinked polymer particles include acrylic monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, styrene monomers such as styrene and alkyl-substituted styrene, and divinylbenzene, Examples include copolymers with crosslinkable monomers such as divinyl sulfone, ethylene glycol dimethacrylate, trimethylolpropane trimethyl acrylate, and pentaerythritol tetramethyl acrylate, melamine resins, benzoguanamine resins, phenol resins, and silicone resins. Among them, (co) polymers of acrylic monomers are preferable.
- the shape of the particles is indefinite, and when the shape is spherical, it is not preferable because scratches on the film or dropping off from the film occur.
- the indefinite form in this invention means shapes other than perfect spherical shape.
- the average particle diameter of the fine particles is preferably 0.5 to 5.0 ⁇ m, more preferably 0.8 to 4.0 ⁇ m. If the average particle size is less than 0.5 ⁇ m, the effect of improving the slipperiness between the film and the metal plate at a high temperature is reduced, and the film may be easily damaged. On the other hand, when the thickness exceeds 5.0 ⁇ m, the above effects may be saturated, the fine particles may be easily removed from the film, the film may be easily broken during film formation, and the impact strength may be reduced.
- the content of the fine particles is preferably 0.5 to 2.0% by mass, more preferably 0.75 to 1.5% by mass in 100% by mass of the composition containing the polyester resin in both the A layer and the B layer. It is. If it is less than 0.5% by mass, the effect of improving the slipperiness between the film and the metal plate at a high temperature is reduced, and the film may be easily damaged. If it exceeds 2.0% by mass, the above effects may be saturated, the film-forming property of the film may be reduced, or the impact strength may be reduced. Further, processing defects of a metal laminate plate in which a film is laminated on a metal plate are detected by appropriately adding cross-linked polymer particles and / or inorganic fine particles with moderate haze, that is, haze of 25 to 60%. It is also possible to prevent malfunction of the defect detector.
- fine particles may be added in the process of producing the polyester resin, or the fine particles may be added and melt-kneaded after preparing the polyester resin composition.
- fine-particles in high concentration can be manufactured, and it can also be melt-kneaded with this as a masterbatch with the polyester-type resin composition which does not contain the said component or contains a small amount.
- the polyester film for metal plate lamination of the present invention contains an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a pigment, an antistatic agent, a lubricant, a crystal nucleating agent, and the like as necessary. be able to.
- each polyester raw material chip to be used is dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer so that the residual moisture content is 150 ppm or less. And extruded into a film at a temperature of 270 to 300 ° C. using an extruder.
- a raw material chip having a residual moisture content exceeding 150 ppm is used, the viscosity of the obtained film is lowered, and troubles such as breakage during production may occur.
- the strength of the film is lowered, and there is a possibility that troubles such as tearing of the film occur when laminating to a metal plate.
- the method for stretching the polyester film of the present invention is not particularly limited, but is preferably a biaxially stretched film.
- biaxial stretching is performed, either a sequential biaxial stretching method or a simultaneous biaxial stretching method may be used, but it is preferable to use the sequential biaxial stretching method because the range of thickness that can be produced is widened.
- the stretching ratio in the machine direction is preferably 2 to 5 times, more preferably 2.5 to 4 times, and the stretching temperature is preferably 80 to 120 ° C., more preferably 90 to 110 ° C. is there.
- the stretching ratio in the transverse direction is preferably 2 to 5 times, more preferably 3 to 4.5 times, and the stretching temperature is preferably 80 to 120 ° C., more preferably 90 to 110 ° C.
- the residual shrinkage stress due to biaxial stretching of the A layer is preferably reduced or removed by a heat setting method or the like. It is because the dimensional change of the film by the heat history in a can manufacturing process etc. can be reduced by doing so.
- the B layer is preferably amorphized or non-orientated due to its thermal history or the like when the residual shrinkage stress is reduced or removed by the A layer being thermally fixed or the like.
- the film is preferably at least 5 ° C. lower than the melting point of the polyester constituting the B layer.
- the temperature is 15 ° C. or lower than the melting point of the polyester constituting the A layer, more preferably 2 ° C. lower than the melting point of the polyester constituting the B layer, and 20 ° C. above the melting point of the polyester constituting the A layer.
- fusing point of A layer and B layer is a temperature which can select the said suitable heat setting temperature.
- the melting point of the A layer means the melting point having the largest crystal melting peak area measured by DSC
- the melting point of the B layer means the polyester resin constituting the layer.
- it means the melting point having the largest crystal melting peak area measured by DSC.
- the film-laminated metal plate of the present invention can be obtained by laminating the polyester film on at least one surface of a metal plate, and has excellent can-making processability.
- the film-laminated metal plate is preferably formed by laminating the B layer of the polyester film on at least one surface of the metal plate.
- the metal plate used for the film laminate metal plate is not particularly limited, and examples thereof include tinplate, tin-free steel, and aluminum. Further, the thickness is not particularly limited, but is preferably 100 to 500 ⁇ m, more preferably 150 to 400 ⁇ m, from the viewpoint of economical efficiency represented by the cost of materials, can manufacturing speed, and the like, while ensuring material strength. It is.
- a known method can be applied, and is not particularly limited, but preferably includes a thermal laminating method, and particularly preferably, the metal plate is energized and heated. There is a method of thermal lamination.
- the said polyester-type film may be laminated on both surfaces of the metal plate. When laminating the polyester film on both surfaces of the metal plate, they may be laminated simultaneously or sequentially.
- the polyester film having a two-layer structure of A layer / B layer on at least one surface of the metal plate it is preferable to use it as a layer for laminating the B layer on the metal plate side.
- a known adhesive mainly composed of a thermosetting resin is applied to the B layer in advance in order to improve the barrier property and corrosion resistance of the B layer and to further improve the laminate adhesion. Lamination may be performed.
- the metal container of the present invention can be obtained by molding using the film laminate metal plate.
- shape of a metal container is not specifically limited, For example, it can be set as a can shape, bottle shape, barrel shape, etc.
- a method for forming the metal container is not particularly limited, and known methods such as a drawing method, an ironing method, and a drawing ironing method can be used.
- the evaluation method and the physical property measurement method for the specimens obtained in each example and comparative example are as follows.
- polyesters (hereinafter referred to as raw material polyesters) as raw materials used in Examples 1 and 2 and Comparative Examples 1 to 5 were heated and melted at 300 ° C. for 5 minutes, and then rapidly cooled with liquid nitrogen. Of the rapidly cooled polyester, 10 mg was used as a sample, and the endothermic peak temperature (melting point) based on crystal melting that appeared when the temperature was raised at a rate of 20 ° C./min was measured. The melting point of the film was also measured in the same manner as the melting point of the raw material polyester, except that samples cut from the A layer and the B layer were used instead of the raw material polyester.
- the glass transition temperature was measured using a differential scanning calorimeter (DSC-60 type) manufactured by Shimadzu Corporation.
- the raw material polyester was melted by heating at 300 ° C. for 5 minutes, and then rapidly cooled with liquid nitrogen. Of the rapidly cooled polyester, 10 mg is used as a sample, the temperature is increased at a rate of 20 ° C./minute, and the glass transition temperature (Tg) is measured from the DSC chart according to the plastic glass transition temperature measurement method described in JIS K 7121. did.
- the glass transition temperature of the film was also measured in the same manner as the glass transition temperature of the raw material polyester, except that a sample cut from the A layer and the B layer was used instead of the raw material polyester.
- Moisture content measuring method The raw material polyester immediately after finishing the drying process was sampled in a container and sealed until the moisture content was measured. About 2 g of this raw material polyester was weighed and measured at a vaporization temperature of 230 ° C. using a moisture measuring device Karl Fischer moisture meter manufactured by Mitsubishi Chemical Analytech.
- the central part on the film surface side of the obtained film laminate metal plate was cut with a razor to a width of 15 mm horizontally with respect to the film laminate traveling direction.
- a film with a width of 15 mm is gradually cut from the film laminate plate while applying water, and peeled about 5 cm in the longitudinal direction.
- the film was set on a Tensilon STM-T-50 manufactured by Baldwin so that the angle between the edge of the peeled film and the film laminated metal plate was 180 °, and the 180 ° peel strength was measured at a tensile speed of 200 mm / min. Thereafter, the preheating temperature is increased from 140 ° C. every 10 ° C., the peel strength is measured in the same manner as described above, and the temperature at which the peel strength is 0.10 N / 15 mm or more is determined as the temperature at which the film can be laminated on the metal plate. It was.
- a 1.5 kg mass slider having a contact area of 50 mm ⁇ 70 mm with the sample as a surface, the film longitudinal stretching direction (in the case of a biaxially stretched film), the film stretching direction (in the case of a uniaxially stretched film), or a film
- the film-forming direction in the case of an unstretched film was set to be parallel to the sliding direction, and the dynamic friction coefficient was measured when sliding on a 80 ° C. tin-free steel plate at a speed of 250 mm / min.
- the preheating temperature of the metal plate at the time of producing the film laminate metal plate was the film laminable temperature measured in (7-2) above.
- Example 1 Manufacture of polyester film
- Resin C PET resin (SU554A manufactured by Toyobo Co., Ltd.) added with agglomerated silica particles (hereinafter referred to as agglomerated silica particles) having an average particle size of 2.7 ⁇ m (SU554A manufactured by Toyobo Co., Ltd.) 50 parts by mass
- Resin D Ge catalyst A copolymer obtained by adding the agglomerated silica particles to a copolymer of terephthalic acid (hereinafter referred to as TPA) / isophthalic acid (hereinafter referred to as IPA) (molar ratio 90/10) and ethylene glycol polymerized in (RF230 manufactured by Toyobo Co., Ltd.).
- TPA terephthalic acid
- IPA isophthalic acid
- Polymerized polyester resin 30 parts by mass Resin E Addition of the above-mentioned aggregated silica particles and polymethyl methacrylate particles (Epester (registered trademark) MA1002 manufactured by Nippon Shokubai Co., Ltd., average particle size 2.0 ⁇ m, refractive index 1.51) to resin C PET resin 20 parts by mass Resin C has an intrinsic viscosity of 0.67 dl / g, a melting point of 254 ° C., and a glass transition point of 76. It was a PET resin at a temperature of 0.2 parts by mass with respect to 100 parts by mass of the resin.
- Resin D is a copolyester resin having an intrinsic viscosity of 0.63 dl / g, a melting point of 233 ° C., and a glass transition point of 70 ° C. In 100 parts by mass of resin, 0.17 parts by mass of the agglomerated silica particles are included. It was.
- Resin E is a PET resin having an intrinsic viscosity of 0.60 dl / g. In 100 parts by mass of the resin, 0.7 parts by mass of the aggregated silica particles and 5.0 parts by mass of the polymethyl methacrylate particles were used.
- Resin J Copolyester resin (RF230 manufactured by Toyobo Co., Ltd.) 90 parts by mass
- Resin K PBT resin (Novaduran (registered trademark) 5007A manufactured by Mitsubishi Engineering Plastics) 10 parts by mass Resin J is a TPA / polymerized with a Ge catalyst.
- Resin K was a PBT resin polymerized with a Ti catalyst, and had an intrinsic viscosity of 0.70 dl / g, a melting point of 222 ° C., and a glass transition point of 30 ° C.
- the polyester for layer A was dried with a paddle dryer. The moisture content after drying was 48 ppm. Next, the dried polyester was melted using a single screw extruder at a resin temperature of 275 ° C. and a residence time of 15 minutes while being fed with a quantitative screw feeder.
- the polyester for the B layer is supplied to each hopper and mixed in the hopper while continuously supplying the funnel-shaped hopper directly above the extruder to the ratio described in the metering screw feeder.
- the resin was melted at a resin temperature of 280 ° C. and a residence time of 15 minutes while removing moisture in the vented extruder without being dried. After this melt was merged in a die, it was extruded onto a cooling drum to form an amorphous sheet.
- the amorphous sheet was stretched 3.5 times in the longitudinal direction at 110 ° C. and 4.1 times in the transverse direction at 130 ° C., and heat-set at 230 ° C. to obtain a layer A thickness of 10.5 ⁇ m and a layer B thickness.
- a polyester film having a thickness of 1.5 ⁇ m (total thickness of 12 ⁇ m), that is, a thickness ratio of each layer, A layer: B layer 87.5: 12.5, was produced. No breakage occurred during film production.
- the haze of the obtained film was measured, it was 51%. Moreover, it was 160 degreeC when the temperature which can be laminated to a metal was measured.
- the dynamic friction coefficient at 80 ° C. of the film-laminated metal plate surface was 0.39.
- the obtained film-laminated metal plate was used for the inner and outer surfaces of the bottom lid and the inner surface of the can body, and was produced as a three-piece can for 185 g. There were no problems such as shrinkage of the film at the joint of the metal container, surface exposure of the metal plate, peeling of the repair tape, and the like. Moreover, the corrosion resistance was also good.
- Table 1 shows the physical properties of the obtained polyester film, the evaluation results of the film laminated metal plate obtained by shaping the polyester film, and the metal container obtained by shaping the film laminated metal plate. .
- Example 2 In Example 1, when the A layer was produced, a mixture of 40 parts by mass of resin C, 24 parts by mass of resin D, and 16 parts by mass of resin E, and a recycled raw material for the polyester-based film obtained in Example 1 (hereinafter, resin F) And 20 parts by mass (containing 10 parts by mass of resin C, 6 parts by mass of resin D, and 4 parts by mass of resin E), and only resin J is used as the resin for the B layer.
- the procedure was the same as Example 1 except that the mass part was used.
- Resin F had an intrinsic viscosity of 0.60 dl / g, a melting point of 248 ° C., a glass transition point of 72 ° C., and a content of units other than the ethylene terephthalate unit and diethylene terephthalate unit was 3.75 mol%.
- polyester for layer A was dried with a separate paddle dryer.
- the moisture contents of the polyethylene terephthalate after drying and the recycled material of the film were 44 ppm and 35 ppm, respectively.
- These dried polyesters are mixed in this hopper while continuously feeding separately to the funnel-shaped hopper directly above the extruder so as to have a ratio determined by a quantitative screw feeder, and the resin temperature is 280 ° C. It was melted using a single screw extruder at a time of 16.5 minutes.
- the polyester for layer B was melted in the same manner as in Example 1. These melts were merged in a die and then extruded onto a cooling drum to form an amorphous sheet. Thereafter, the amorphous sheet is stretched 3.5 times in the longitudinal direction at 110 ° C.
- a film-laminated metal plate was obtained in the same manner as in Example 1. At this time, there was no problem in handling properties such as film breakage, and the film was good. Moreover, the block copolymer in a film did not adhere to a rubber roll, and high-speed can-making property was also favorable.
- the dynamic friction coefficient at 80 ° C. of the surface of the film laminate metal plate was 0.40.
- Table 1 shows the physical properties of the obtained polyester film, the evaluation results of the film laminated metal plate obtained by shaping the polyester film, and the metal container obtained by shaping the film laminated metal plate. .
- Example 1 In Example 1, the same procedure as in Example 1 was performed except that 76 parts by mass of resin C, 20 parts by mass of resin E, and 4 parts by mass of resin G described below were mixed and used. There was no breakage during film production.
- Resin G In a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade, 75 parts by mass of 1,4-butanediol, 100 parts by mass of dimethyl terephthalate, 75 parts by mass of tetramethylene glycol (weight average molecular weight 1000) and 0.05 parts by mass of normal butyl titanate were charged, and transesterification was carried out while distilling methanol produced at 190 ° C to 230 ° C out of the system.
- polytetramethylene terephthalate-polytetramethylene oxide block copolymer had a polytetramethylene oxide ratio of 40 mass% and an intrinsic viscosity of 1.90 dl / g.
- the haze of the obtained film was measured, it was 55%. It was 160 degreeC when the temperature which can be laminated to a metal was measured.
- the film-laminated metal plate of the polyester film there was no problem in handling properties, such as film breakage, and it was good, but there was a problem that the block copolymer in the film adhered to the entire rubber roll. It was seen.
- the dynamic friction coefficient at 80 ° C. of the surface of the film laminate metal plate was 0.35.
- evaluation of high-speed can-making property and manufacture / evaluation of a metal container were not performed.
- Table 1 shows the physical properties of the obtained polyester film and the evaluation results of the film-laminated metal plate obtained by molding the polyester film.
- Example 2 In Example 1 above, when producing the A layer, without using the resin D, 65 parts by mass of the resin C, 20 parts by mass of the resin E, and NOVADURAN (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., which is a PBT resin The procedure was the same as Example 1 except that 15 parts by mass of 5020HF (hereinafter referred to as resin H) was used. No breakage occurred during film production.
- Resin H was a PBT resin having an intrinsic viscosity of 1.20 dl / g, a melting point of 224 ° C., and a glass transition point of 30 ° C.
- polyester for layer A was dried with a separate paddle dryer.
- the moisture contents of the polyethylene terephthalate after drying and the recycled material of the film were 38 ppm and 39 ppm, respectively.
- These dried polyesters were mixed in this hopper while continuously feeding separately to the funnel-shaped hopper directly above the extruder so as to have a ratio determined by a quantitative screw feeder, and the resin temperature was 285 ° C. It was melted using a single screw extruder at a time of 15.7 minutes.
- the polyester for layer B was melted in the same manner as in Example 1. These melts were merged in a die and then extruded onto a cooling drum to form an amorphous sheet. Thereafter, the amorphous sheet was stretched 3.5 times in the longitudinal direction at 110 ° C.
- a polyester film having a thickness of 1.5 ⁇ m (total thickness of 12 ⁇ m), that is, a thickness ratio of each layer, A layer: B layer 87.5: 12.5, was produced. No breakage occurred during film production.
- the haze of the obtained film was measured, it was 50%. Moreover, it was 160 degreeC when the temperature which can be laminated to a metal was measured.
- a film-laminated metal plate was obtained in the same manner as in Example 1. At this time, there was no problem in handling properties such as film breakage, and the film was good. Moreover, the block copolymer in a film did not adhere to a rubber roll, and high-speed can-making property was also favorable.
- the dynamic friction coefficient at 80 ° C. of the film-laminated metal plate surface was 0.39.
- Table 1 shows the physical properties of the obtained polyester film, the evaluation results of the film laminated metal plate obtained by shaping the polyester film, and the metal container obtained by shaping the film laminated metal plate. .
- Example 3 In Example 1, when the A layer was produced, a film was produced under the same conditions as in Example 1 except that 80 parts by mass of resin C and 20 parts by mass of resin E were used without using resin D. . No breakage occurred during film production.
- a film-laminated metal plate was obtained in the same manner as in Example 1. At this time, there was no problem in handling properties such as film breakage, and the film was good. Moreover, the block copolymer in a film did not adhere to a rubber roll, and high-speed can-making property was also favorable.
- the dynamic friction coefficient at 80 ° C. of the surface of the film laminate metal plate was 0.35.
- Table 1 shows the physical properties of the obtained polyester film, the evaluation results of the film laminated metal plate obtained by shaping the polyester film, and the metal container obtained by shaping the film laminated metal plate. .
- Example 4 In Example 1, when the A layer was produced, the aggregated silica particles in the copolymer of TPA / IPA (molar ratio 88/12) and ethylene glycol were 0.80 parts by mass in 100 parts by mass of the resin.
- Resin I 100 parts by mass of the copolyester resin added to the resin
- the same procedure as in Example 1 was carried out except that 100 parts by mass of Resin I was used.
- a film was produced under the same conditions as in Example 1 except that the heat setting temperature of was changed to 210 ° C. No breakage occurred during film production.
- Resin I was a copolyester resin having an intrinsic viscosity of 0.63 dl / g, a melting point of 229 ° C., and a glass transition point of 76 ° C.
- a film-laminated metal plate was obtained in the same manner as in Example 1. However, soiling occurred in the laminating process, and scratches also occurred in the can manufacturing process. The dynamic friction coefficient at 80 ° C. of the surface of the film laminate metal plate was 0.43.
- Table 1 shows the physical properties of the obtained polyester film, the evaluation results of the film laminated metal plate obtained by shaping the polyester film, and the metal container obtained by shaping the film laminated metal plate. .
- Example 5 In Example 1, 100 parts by mass of the resin D was used when the A layer was produced, and the copolymer of TPA / IPA (molar ratio 78/22) and ethylene glycol was used when the B layer was produced. Example 1 was used except that only 100 parts by mass of a copolyester resin added so that the aggregated silica particles were 0.8 parts by mass in 100 parts by mass of the resin (hereinafter referred to as resin L) was used. A film was prepared. No breakage occurred during film production. Resin L was a copolyester resin having an intrinsic viscosity of 0.63 dl / g, a melting point of 200 ° C., and a glass transition point of 74 ° C.
- a film-laminated metal plate was obtained in the same manner as in Example 1. However, soiling occurred in the laminating process, and scratches also occurred in the can manufacturing process. The dynamic friction coefficient at 80 ° C. of the surface of the film laminate metal plate was 0.43.
- Table 1 shows the physical properties of the obtained polyester film, the evaluation results of the film laminated metal plate obtained by shaping the polyester film, and the metal container obtained by shaping the film laminated metal plate. .
- the polyester film for laminating a metal plate of the present invention has excellent corrosion resistance and can be bonded to a metal plate at a low temperature. Therefore, it has excellent can-making properties (for example, bending, joining, joint repair, flanging, top lid attachment, content filling, bottom lid attachment, retort sterilization), and the present invention includes coffee beverages, soft drinks, canned foods, etc. It can be used for a wide range of metal containers and contributes to the industry.
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Abstract
Description
A層は、エチレンテレフタレートを主としたポリエステル系樹脂を含む組成物から形成されている。具体的には、A層を構成する樹脂は、ポリエステルの全構成ユニット100モル%中、エチレンテレフタレートユニット及びジエチレンテレフタレートユニットの合計含有量が95モル%以上98モル%以下であるポリエステル系樹脂である。エチレンテレフタレートユニット及びジエチレンテレフタレートユニットの合計含有量が95モル%未満の場合は、耐熱性に劣るおそれがある。また、製缶時にフィルムに高温の熱処理を行った場合、縮みや剥がれ等のトラブルが生ずるおそれがある。なお、ポリエステルの構成ユニットとしては、エチレンテレフタレートユニット又はジエチレンテレフタレートユニットの一方しか含まれていなくてもよい。
B層は、エチレンテレフタレートを主としたポリエステル系樹脂を含む組成物から形成されている。B層を構成する樹脂は、エチレンテレフタレートを主としたポリエステル系樹脂(以下、樹脂B1という)80~100質量%と、樹脂B1とは異なる組成を有するポリエステル系樹脂(以下、樹脂B2という)0~20質量%とからなる。好ましくは、B層は、85~95質量%の樹脂B1と、5~15質量%の樹脂B2とからなるポリエステル系樹脂である。
不定形無機粒子を形成する材料として例えば、シリカ、アルミナ、ジルコニア、酸化チタン等の金属酸化物;カオリン、ゼオライト、セリサイト、セピオライト等の複合酸化物;硫酸カルシウム、硫酸バリウム等の硫酸塩;リン酸カルシウム、リン酸ジルコニウム等のリン酸塩;炭酸カルシウム等の炭酸塩等を挙げることができ、中でも金属酸化物であることが好ましい。これらの無機微粒子は天然品であっても合成品であってもよい。
また、架橋高分子粒子としては、例えば、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル等のアクリル系単量体、スチレンやアルキル置換スチレン等のスチレン系単量体等と、ジビニルベンゼン、ジビニルスルホン、エチレングリコールジメタクリレート、トリメチロールプロパントリメチルアクリレート、ペンタエリスリトールテトラメチルアクリレート等の架橋性単量体との共重合体、メラミン系樹脂、ベンゾグアナミン系樹脂、フェノール系樹脂、シリコーン系樹脂等を挙げることができ、中でもアクリル系単量体の(共)重合体であることが好ましい。
本発明のポリエステル系フィルムの製造方法としては、使用する各ポリエステルの原料チップにおいて、残留する水分率が150ppm以下になるようにホッパドライヤー、パドルドライヤー等の乾燥機、又は真空乾燥機を用いて乾燥し、押出機を用いて270~300℃の温度でフィルム状に押出す。残留する水分率が150ppmを超えた原料チップを使用すると得られたフィルムの粘度が低下し、製造時破断等のトラブルが発生するおそれがある。また、フィルムの強度が低下し、金属板にラミネートする際にフィルムが破れる等のトラブルが発生するおそれもある。上記以外の製造方法として、未乾燥のポリエステル原料チップをベント式押出機内で水分を除去しながら270~300℃の温度でフィルム状に押出す方法がある。押出しに際してはTダイ法、チューブラ法等、公知のどの方法を採用しても構わない。押出し後は、急冷して未延伸フィルムを得る。
本発明のフィルムラミネート金属板は、上記ポリエステル系フィルムを金属板の少なくとも片面にラミネートして得ることができるものであって、製缶加工性に優れたものである。フィルムラミネート金属板は、上記ポリエステル系フィルムのB層が、金属板の少なくとも一方の面にラミネートされてなることが好ましい。
粒度分布計(堀場製作所社製SZ-100)を用いて無機微粒子の平均粒径を測定した。
島津製作所社製DSC-60型示差走査熱量計を用いて測定した。実施例1・2、比較例1~5で用いられる原材料としてのポリエステル(以下、原料ポリエステルという)を300℃で5分間加熱溶融した後、液体窒素で急冷した。急冷したポリエステルのうち、10mgを試料とし、20℃/分の速度で昇温していった際に現れる結晶融解に基づく吸熱ピーク温度(融点)を測定した。フィルムの融点についても、原料ポリエステルの代わりにA層、B層から削り取ったサンプルを用いた以外は原料ポリエステルの融点と同様に測定した。
島津製作所社製示差走査型熱量計(DSC-60型)を用いて測定を行った。原料ポリエステルを300℃で5分間加熱溶融した後、液体窒素で急冷した。急冷したポリエステルのうち、10mgを試料とし、20℃/分の速度で昇温して、そのDSCチャートからJIS K 7121に記載のプラスチックのガラス転移温度測定方法に従って、ガラス転移温度(Tg)を測定した。フィルムのガラス転移温度についても、原料ポリエステルの代わりにA層、B層から削り取ったサンプルを用いた以外は原料ポリエステルのガラス転移温度と同様に測定した。
試料約30mgをクロロホルムD(ユーリソップ社製)とトリフルオロ酢酸D1(ユーリソップ社製)を10:1(体積比)で混合した溶媒に溶解させて、試料溶液を調製した。そして、核磁気共鳴(NMR)装置(Varian社製GEMINI-200)を用いて、温度23℃、積算回数64回の測定条件で試料溶液のプロトンのNMRを測定した。NMR測定では、所定のプロトンのピーク強度を算出して、酸成分100モル%中のテレフタル酸成分およびイソフタル酸成分の含有率(モル%)を算出した。
フェノール(60質量%)と1,1,2,2-テトラクロロエタン(40質量%)との混合溶媒に、原料ポリエステルを濃度0.4g/dlとなるように溶解し、ウベローデ型粘度管を用いて温度30℃で測定した。極限粘度の単位はdl/gである。
乾燥過程を終了した直後の原料ポリエステルを容器にサンプリングし、水分率測定まで密封しておいた。この原料ポリエステルを約2g秤量し、三菱化学アナリテック社製の水分測定装置カールフィッシャー水分計を用いて、気化温度230℃で測定した。
(7-1)ヘイズの測定方法
JIS K 7136に準拠し、ヘイズメーター(日本電色工業社製300A)を用いて測定した。なお、測定は2回行い、その平均値を求めた。
脱脂処理した厚さ190μmの金属板(ティンフリースチール、Lタイプブライト仕上げ、表面粗さ0.3~0.5μm、新日鐵住金社製)を140℃に予熱しておき、金属板とA層及びB層の2層で構成されているポリエステル系フィルムのB層表面とを合わせ、ゴムロールとゴムロールとの間を圧力を500N/cmで速度10m/分の条件で貼り合わせたものを通過させ、その後、急水冷させてフィルムラミネート金属板〔厚さ202μm(ポリエステル系フィルム/金属板=12μm/190μm)〕を得た。
得られたフィルムラミネート金属板のフィルム面側の中央部をフィルムラミネート進行方向に対して水平に15mm幅にカミソリでカットした。水を付けながらフィルムラミネート板から徐々に15mm幅部分のフィルムをカットし、長手方向に5cm程度剥離させる。剥離させたフィルムの端部とフィルムラミネート金属板との角度が180°になるようにボールドウィン社製のテンシロンSTM-T-50にセットし、引張速度200mm/分で180°剥離強度を測定した。
その後、予熱温度を140℃から10℃毎に昇温して、上記と同様に剥離強度の測定を行い、剥離強度が0.10N/15mm以上となった温度を金属板へのフィルムラミネート可能温度とした。
日立製作所社製透過型電子顕微鏡(HU-12型)を用いて、ポリエステル系フィルムの超薄断面切片を観察し、フィルム各層の厚み(μm)を測定した。
(8-1)動摩擦係数の測定方法
上記(7-2)のようにして得られるフィルムラミネート金属板を、長辺がフィルム縦延伸方向(二軸延伸フィルムの場合)、フィルム延伸方向(一軸延伸フィルムの場合)、又はフィルム製膜方向(未延伸フィルムの場合)に対して平行となるように150mm×100mmの長方形に裁断して試料とした。次いで、50mm×70mmの接触面積を有する質量1.5kgの滑走子に該試料を表面にしてフィルム縦延伸方向(二軸延伸フィルムの場合)、フィルム延伸方向(一軸延伸フィルムの場合)、又はフィルム製膜方向(未延伸フィルムの場合)が滑走方向と平行となるようセットし、80℃のティンフリースチール板上を速度250mm/分で滑走させたときの動摩擦係数を測定した。なお、フィルムラミネート金属板作製時の金属板の予熱温度は上記(7-2)で測定したフィルムラミネート可能温度とした。
上記(7-2)のようにしてフィルムラミネート金属板を作製した後にゴムロールに異物が付着しているか否かを目視で確認した。
A:汚れが確認できない
B:汚れが部分的に付着
C:汚れが全体に付着
上記(7-2)のようにして得られたフィルムラミネート金属板を、底蓋、缶胴、及び上蓋に用い、185g用の3ピース缶として製缶した。製缶後に当該フィルムの表面におけるスクラッチ傷の有無について観察を行った。
A:傷が確認できない
B:薄く傷が見える
C:傷が見える
(9-1)補修でのフィルムの収縮・剥がれ
上記(8-3)のようにして得られた金属容器(3ピース缶)の接合部の補修をエポキシ樹脂補修テープを用いて行った。接合補修部におけるフィルムの外観を目視で観察した。
A:外観の変化無し
B:フィルムの収縮によるズレあり
C:フィルムの収縮による剥がれあり
上記(9-1)のようにして金属容器(3ピース缶)の接合部の補修を行った。接合補修部におけるエポキシ樹脂補修テープの外観を目視で観察した。
A:外観の変化無し
B:補修テープの浮きがあり
C:補修テープの剥がれあり
上記(7-2)のようにして得られるフィルムラミネート金属板を用いて、フィルムラミネート面が内側になるように350ml用の3ピース缶を製缶し、得られた3ピース缶の内容物として、5質量%の食塩を含有する炭酸水(炭酸ガス濃度1000ppm)を充填して、140℃で10分間のレトルト処理を実施した後、80℃で2週間保存する。その後、充填された炭酸水を抜き出し、缶を切り開き、水洗いした後のフィルムラミネート面を観察し、以下に示す基準に基づき耐腐食性を判定した。
A:フィルム表面の変色が観察されない
B:フィルム表面の変色が観察される
(ポリエステル系フィルムの製造)
A層用の樹脂として、以下の3種類の樹脂C~Eの混合物を用いた。
樹脂C:平均粒径2.7μmの凝集タイプのシリカ粒子(以下、凝集シリカ粒子という)(富士シリシア社製 サイリシア310)を添加したPET樹脂(東洋紡社製SU554A) 50質量部
樹脂D:Ge触媒で重合したテレフタル酸(以下、TPAという)/イソフタル酸(以下、IPAという)(モル比90/10)とエチレングリコールとの共重合体(東洋紡社製RF230)に上記凝集シリカ粒子を添加した共重合ポリエステル系樹脂 30質量部
樹脂E:樹脂Cにさらに上記凝集シリカ粒子及びポリメタクリル酸メチル粒子(日本触媒社製エポスター(登録商標)MA1002、平均粒径2.0μm 屈折率1.51)を添加したPET樹脂 20質量部
樹脂Cは、極限粘度が0.67dl/g、融点が254℃、ガラス転移点が76℃のPET樹脂であり、樹脂100質量部中、上記凝集シリカ粒子0.2質量部であった。
樹脂Dは、極限粘度が0.63dl/g、融点が233℃、ガラス転移点が70℃の共重合ポリエステル系樹脂であり、樹脂100質量部中、上記凝集シリカ粒子0.17質量部であった。
樹脂Eは、極限粘度が0.60dl/gのPET樹脂であり、樹脂100質量部中、上記凝集シリカ粒子0.7質量部、上記ポリメタクリル酸メチル粒子5.0質量部であった。
樹脂J:共重合ポリエステル系樹脂(東洋紡社製RF230) 90質量部
樹脂K:PBT樹脂(三菱エンジニアリングプラスチックス社製ノバデュラン(登録商標)5007A) 10質量部
樹脂Jは、Ge触媒で重合したTPA/IPA(モル比90/10)とエチレングリコールとの共重合ポリエステル系樹脂であって、極限粘度が0.63dl/g、融点が233℃、ガラス転移点が70℃であった。また、樹脂Kは、Ti触媒で重合したPBT樹脂であって、極限粘度が0.70dl/g、融点が222℃、ガラス転移点が30℃であった。
脱脂処理した厚さ190μmの金属板(ティンフリースチール、Lタイプブライト仕上げ、表面粗さ0.3~0.5μm、新日鐵住金社製)を上記(7-2)で測定した金属板へのフィルムラミネート可能温度に予熱しておき、金属板とポリエステル系フィルムのB層表面とを合わせ、ゴムロールとゴムロールとの間を圧力を500N/cmで速度10m/分の条件で貼り合わせたものを通過させ、その後、急水冷させてフィルムラミネート金属板〔厚さ202μm(ポリエステル系フィルム/金属板=12μm/190μm)〕を得た。このときにフィルムの破断等、ハンドリング性に問題は生じず、良好なものであった。また、ゴムロールにフィルム中のブロック共重合物が付着せず、高速製缶性も良好であった。フィルムラミネート金属板表面の80℃での動摩擦係数は0.39であった。
得られたフィルムラミネート金属板を、底蓋の内外面及び缶胴の内面に用い、185g用の3ピース缶として製缶した。金属容器の接合部のフィルムの収縮や金属板の表面露出、補修テープの剥がれ等の問題は生じなかった。また、耐腐食性も良好であった。
実施例1において、A層を作製する際に、樹脂C40質量部、樹脂D24質量部、及び樹脂E16質量部の混合物と、実施例1で得られたポリエステル系フィルムの再生原料(以下、樹脂Fとする)20質量部(樹脂Cが10質量部、樹脂Dが6質量部、樹脂Eが4質量部含まれている)との混合物を用い、B層用の樹脂として、樹脂Jのみを100質量部用いた以外は実施例1と同様にした。樹脂Fは、極限粘度が0.60dl/g、融点が248℃、ガラス転移点が72℃、エチレンテレフタレートユニット及びジエチレンテレフタレートユニット以外のユニットの含有量が3.75モル%であった。
実施例1と同様にフィルムラミネート金属板を得た。このときにフィルムの破断等、ハンドリング性に問題は生じず、良好なものであった。また、ゴムロールにフィルム中のブロック共重合物が付着せず、高速製缶性も良好であった。フィルムラミネート金属板表面の80℃での動摩擦係数は0.40であった。
実施例1と同様に185g用の3ピース缶として製缶した。金属容器の接合部のフィルムの収縮や金属板の表面露出、補修テープの剥がれ等の問題は生じなかった。また、耐腐食性も良好であった。
上記実施例1において、A層を作製する際に、樹脂C76質量部、樹脂E20質量部、及び以下に記載の樹脂G4質量部を混合して用いた以外は実施例1と同様にした。フィルム製造時に破断はなかった。
樹脂G:投入口、温度計、圧力計及び精留塔付留出管、撹拌翼を備えた反応装置に、テレフタル酸ジメチル100質量部に対して、1,4-ブタンジオール75質量部、ポリテトラメチレングリコール(重量平均分子量1000)75質量部、ノルマルブチルチタネート0.05質量部を仕込み、190℃~230℃で生成するメタノールを系外に留出しながらエステル交換反応を行った。反応終了後、テトラノルマルブチルチタネート0.05質量部、およびリン酸0.025質量部を添加し250℃、減圧下(1.0hPa以下)で重縮合反応を行い、ポリテトラメチレンテレフタレート-ポリテトラメチレンオキサイドブロック共重合体を得た。得られたポリテトラメチレンテレフタレート-ポリテトラメチレンオキサイドブロック共重合体は、ポリテトラメチレンオキサイドの比率40質量%、極限粘度1.90dl/gであった。
上記実施例1において、A層を作製する際に、樹脂Dを用いずに、樹脂Cを65質量部、樹脂Eを20質量部、PBT樹脂である三菱エンジニアリングプラスチックス社製ノバデュラン(登録商標)5020HF(以下、樹脂Hという)を15質量部用いた以外は実施例1と同様にした。フィルム製造時に破断は生じなかった。
また、樹脂Hは、極限粘度が1.20dl/g、融点が224℃、ガラス転移点が30℃のPBT樹脂であった。
実施例1と同様にフィルムラミネート金属板を得た。このときにフィルムの破断等、ハンドリング性に問題は生じず、良好なものであった。また、ゴムロールにフィルム中のブロック共重合物が付着せず、高速製缶性も良好であった。フィルムラミネート金属板表面の80℃での動摩擦係数は0.39であった。
実施例1と同様に185g用の3ピース缶として製缶した。金属容器の接合部のフィルムの収縮や金属板の表面露出、補修テープの剥がれ等の問題は生じなかった。しかし、耐腐食性評価を行ったところ、フィルム表面に変色が生じており、問題があった。
実施例1において、A層を作製する際に、樹脂Dを用いずに、樹脂Cを80質量部、樹脂Eを20質量部用いた以外は、実施例1と同様の条件でフィルムを作製した。フィルム製造時に破断は生じなかった。
実施例1と同様にフィルムラミネート金属板を得た。このときにフィルムの破断等、ハンドリング性に問題は生じず、良好なものであった。また、ゴムロールにフィルム中のブロック共重合物が付着せず、高速製缶性も良好であった。フィルムラミネート金属板表面の80℃での動摩擦係数は0.35であった。
実施例1と同様に185g用の3ピース缶として製缶した。金属容器の接合部のフィルムの収縮や金属板の表面露出はなかったが、補修テープの剥がれが生じた。
実施例1において、A層を作製する際に、TPA/IPA(モル比88/12)とエチレングリコールとの共重合体に上記凝集シリカ粒子が樹脂100質量部中0.80質量部となるように添加された共重合ポリエステル系樹脂(以下、樹脂Iとする)を100質量部用い、B層を作製する際に、樹脂Iを100質量部用いた以外は実施例1と同様にし、延伸後の熱固定温度を210℃に変更した以外は、実施例1と同様の条件でフィルムを作製した。フィルム製造時に破断は生じなかった。また、樹脂Iは、極限粘度が0.63dl/g、融点が229℃、ガラス転移点が76℃の共重合ポリエステル系樹脂であった。
実施例1と同様にフィルムラミネート金属板を得た。しかし、ラミネート工程において汚れが生じ、製缶工程においても傷が生じた。フィルムラミネート金属板表面の80℃での動摩擦係数は0.43であった。
実施例1と同様に185g用の3ピース缶として製缶した。金属容器の接合部の補修の際に、フィルムのB層の溶融による剥がれ及びA層収縮によるフィルムのズレが発生し、補修できなかった。
実施例1において、A層を作製する際に、樹脂Dのみを100質量部用い、B層を作製する際に、TPA/IPA(モル比78/22)とエチレングリコールとの共重合体に上記凝集シリカ粒子が樹脂100質量部中0.8質量部となるように添加された共重合ポリエステル系樹脂(以下、樹脂Lとする)のみを100質量部用いた以外は実施例1と同様にしてフィルムを作製した。フィルム製造時に破断は生じなかった。また、樹脂Lは、極限粘度が0.63dl/g、融点が200℃、ガラス転移点が74℃の共重合ポリエステル系樹脂であった。
実施例1と同様にフィルムラミネート金属板を得た。しかし、ラミネート工程において汚れが生じ、製缶工程においても傷が生じた。フィルムラミネート金属板表面の80℃での動摩擦係数は0.43であった。
実施例1と同様に185g用の3ピース缶として製缶した。金属容器の接合部の補修の際に、フィルムのB層の溶融による剥がれが発生し、補修できなかった。
Claims (9)
- A層及びB層の2層で構成されるポリエステル系フィルムであって、
A層を構成する樹脂は、ポリエステルの全構成ユニット100モル%中、エチレンテレフタレートユニット及びジエチレンテレフタレートユニットの合計含有量が95モル%以上98モル%以下であるポリエステル系樹脂であり、
B層を構成する樹脂は、エチレンテレフタレートを主としたポリエステル系樹脂(B1)80~100質量%と、上記ポリエステル系樹脂(B1)とは異なる組成を有するポリエステル系樹脂(B2)0~20質量%とからなる
ことを特徴とする金属板ラミネート用ポリエステル系フィルム。 - 上記A層を構成する樹脂は、ポリエステルの全構成ユニット100モル%中、エチレンイソフタレートユニットが2モル%以上5モル%以下である請求項1に記載の金属板ラミネート用ポリエステル系フィルム。
- A層とB層の厚み比率が75:25~95:5である請求項1又は2に記載の金属板ラミネート用ポリエステル系フィルム。
- 上記ポリエステル系樹脂(B1)は、ポリエステルの全構成ユニット100モル%中、エチレンイソフタレートユニットが5モル%以上15モル%以下である1~3のいずれか1項に記載の金属板ラミネート用ポリエステル系フィルム。
- 上記ポリエステル系樹脂(B1)が、ポリエチレンテレフタレート及びポリエチレンイソフタレートからなる請求項1~4のいずれか1項に記載の金属板ラミネート用ポリエステル系フィルム。
- 上記ポリエステル系樹脂(B2)が、ポリブチレンテレフタレートである請求項1~5のいずれか1項に記載の金属板ラミネート用ポリエステル系フィルム。
- B層と金属板とのラミネート可能温度が200℃以下である請求項1~6のいずれか1項に記載の金属板ラミネート用ポリエステル系フィルム。
- 請求項1~7のいずれか1項に記載のポリエステル系フィルムのB層が、金属板の少なくとも一方の面にラミネートされてなるフィルムラミネート金属板。
- 請求項8に記載のフィルムラミネート金属板を成形してなる金属容器。
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JP2006326902A (ja) * | 2005-05-24 | 2006-12-07 | Nippon Steel Corp | 容器用複層ポリエステルフィルムラミネート金属板及びその製造方法 |
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2016
- 2016-03-09 WO PCT/JP2016/057358 patent/WO2016143817A1/ja active Application Filing
- 2016-03-09 JP JP2017505375A patent/JP6760261B2/ja active Active
- 2016-03-09 US US15/556,961 patent/US20180050518A1/en not_active Abandoned
- 2016-03-09 EP EP16761784.4A patent/EP3269549B1/en active Active
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JP2006289989A (ja) * | 1999-11-05 | 2006-10-26 | Toyobo Co Ltd | 金属板ラミネート用ポリエステル系フィルム、フィルムラミネート金属板および金属容器 |
JP2002193255A (ja) * | 2000-12-25 | 2002-07-10 | Mitsubishi Materials Corp | ラミネート缶蓋 |
JP2004122577A (ja) * | 2002-10-02 | 2004-04-22 | Mitsubishi Alum Co Ltd | ポリエステル樹脂被覆アルミニウム合金板 |
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CN115298025A (zh) * | 2020-04-03 | 2022-11-04 | 东洋钢钣株式会社 | 层叠聚酯树脂被覆金属板、层叠聚酯树脂膜和罐盖 |
Also Published As
Publication number | Publication date |
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JP6760261B2 (ja) | 2020-09-23 |
EP3269549A4 (en) | 2018-08-29 |
EP3269549B1 (en) | 2019-12-18 |
US20180050518A1 (en) | 2018-02-22 |
EP3269549A1 (en) | 2018-01-17 |
JPWO2016143817A1 (ja) | 2017-12-21 |
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