WO2016136099A1 - Plaque métallique revêtue de résine, procédé de production d'une plaque métallique revêtue de résine, et récipient métallique - Google Patents

Plaque métallique revêtue de résine, procédé de production d'une plaque métallique revêtue de résine, et récipient métallique Download PDF

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WO2016136099A1
WO2016136099A1 PCT/JP2015/085028 JP2015085028W WO2016136099A1 WO 2016136099 A1 WO2016136099 A1 WO 2016136099A1 JP 2015085028 W JP2015085028 W JP 2015085028W WO 2016136099 A1 WO2016136099 A1 WO 2016136099A1
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Prior art keywords
resin
metal plate
amount
coating layer
phr
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PCT/JP2015/085028
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English (en)
Japanese (ja)
Inventor
安秀 大島
北川　淳一
克己 小島
中村　紀彦
裕樹 中丸
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Ｊｆｅスチール株式会社
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Priority to JP2016534749A priority Critical patent/JPWO2016136099A1/ja
Publication of WO2016136099A1 publication Critical patent/WO2016136099A1/fr

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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
    • 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
    • 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
    • B65D1/12—Cans, casks, barrels, or drums
    • B65D1/14—Cans, casks, barrels, or drums characterised by shape
    • B65D1/16—Cans, casks, barrels, or drums characterised by shape of curved cross-section, e.g. cylindrical

Definitions

  • the present invention relates to a resin-coated metal plate provided with a resin film layer on both surfaces of the metal plate, a method for producing the resin-coated metal plate, and a metal container.
  • a two-piece can is a metal container composed of two parts, a can body integrated with a can bottom and a lid.
  • a three-piece can is a metal container composed of three parts: a can body, an upper lid, and a bottom lid.
  • a two-piece can body has a beautiful appearance because it does not have a seam portion (welded portion), but is manufactured by a drawing method or the like, and therefore generally requires a high degree of processing.
  • the can body of the three-piece can has a seam portion, so that the appearance is inferior to that of the two-piece can body, but a high degree of processing is not necessary.
  • the degree of processing increases as the capacity of the metal container increases, so generally two-piece cans are used for small-capacity metal containers and three-piece for large-capacity metal containers. Cans tend to be used.
  • the inventors of the present invention use a resin-coated metal plate to form a two-piece can body having a high degree of processing, the adhesion between the processed resin film layer and the metal plate, and the inner surface of the metal container after the forming process.
  • heat treatment for the purpose of improving the covering property of the resin coating layer located on the side and the design property of the resin coating layer on the outer surface side of the metal container after the molding process, forming into the resin coating layer on the surface side It has been found that defects in appearance due to scratches and micro unevenness occur. For this reason, in order to manufacture a two-piece can body having a high degree of processing using a resin-coated metal plate, it is necessary to prevent appearance defects from being caused by molding and heat treatment.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a resin-coated metal plate, a method for producing a resin-coated metal plate, and a metal that can suppress appearance defects due to molding and heat treatment. To provide a container.
  • the inventors of the present invention have intensively studied, and as a result, have found that molding flaws are caused by insufficient slidability between the tool and the resin coating layer during molding.
  • defects in appearance caused by heat treatment are caused by the residual stress in the resin coating layer generated during the molding process being relaxed by the heat treatment, causing the resin coating layer to deform non-uniformly, resulting in non-uniform pigment formation. It was found that this occurs because the distribution is formed.
  • the inventors of the present invention have suppressed molding flaws by adding wax to the resin coating layer, and the micro unevenness after heat treatment has a specific resin composition.
  • the inventors have come up with a technical idea that the resin film layer can be controlled by reducing the residual stress of the resin film layer after molding by controlling the crystallinity of the resin film layer.
  • the resin-coated metal plate according to the present invention is a resin-coated metal plate provided with a resin film layer on both surfaces of the metal plate, and the resin film layer located on the outer surface side of the container after molding processing has an ethylene terephthalate unit of 97 mol% or more. 1J in terms of the difference between the amount of heat of crystallization and the amount of heat of fusion after being coated on a metal plate, containing a wax component in the range of 0.05 PHR to 5 PHR, based on resin. / G or more and 20 J / g or less.
  • the resin coating layer located on the outer surface side of the container after the molding process contains 5 PHR or more and 30 PHR or less of titanium oxide.
  • the resin coating layer located on the outer surface side of the container after molding has a structure of two or more layers, and the resin coating layers of each layer are mainly composed of a resin having an ethylene terephthalate unit of 97 mol% or more, and from 1 ⁇ m to 5 ⁇ m from the outermost surface. It has a layer containing the following wax components, and the amount of wax relative to the amount of resin in the layer containing wax and the amount of wax relative to the resin amount of the entire resin coating layer are both in the range of 0.05 PHR to 5 PHR.
  • the difference between the heat of crystallization and the heat of fusion of the resin film layer after being coated on the metal plate is preferably in the range of 1 J / g or more and 20 J / g or less in terms of unit weight.
  • the resin coating layer located on the outer surface side of the container after molding has a structure of two or more layers, and the resin coating layers of each layer are mainly composed of a resin having an ethylene terephthalate unit of 97 mol% or more, and from 1 ⁇ m to 5 ⁇ m from the outermost surface. It has a layer containing the following wax components, and the amount of wax relative to the amount of resin in the outermost surface layer containing wax and the amount of wax relative to the amount of resin in the entire resin coating layer are both in the range of 0.05 PHR to 5 PHR.
  • the amount of titanium oxide with respect to the resin amount of the entire resin coating layer is in the range of 5 PHR to 30 PHR, and at least at a depth of 1 ⁇ m from the outermost surface, the amount of titanium oxide is in the range of 2 PHR or less,
  • the difference between the heat of crystallization and the heat of fusion of the resin coating layer after being coated on the plate is in the range of 1 J / g or more and 20 J / g or less in terms of unit weight. It is preferred that in.
  • the resin coating layer located on the outer surface side of the container after molding has a structure of three or more layers consisting of an outermost surface layer, at least one intermediate layer, and the lowermost layer, and each resin coating layer is 97 mol of ethylene terephthalate unit.
  • the amount of wax relative to the amount of resin is in the range of 0.05 PHR to 5 PHR, and the difference between the heat of crystallization and the heat of fusion of the resin coating layer after being coated on the metal plate is 1J in terms of unit weight. / G or more and 20 J / g or less is preferable.
  • the amount of titanium oxide with respect to the resin amount of the entire resin coating layer is in the range of 5 PHR to 30 PHR, and the amount of titanium oxide in the range of at least 1 ⁇ m from the outermost surface and 1 ⁇ m from the lowermost surface is 2 PHR or less. It is preferable to be within.
  • the difference between the amount of heat of crystallization and the amount of heat of fusion after the resin coating layer located on the inner surface side of the container after molding is coated on the metal plate is in the range of 1 J / g or more and 20 J / g or less in terms of unit weight. It is preferable that it is formed of the resin material inside.
  • the resin coating layer located on the inner surface side of the container after the molding process is formed of a resin material having an ethylene terephthalate unit of 97 mol% or more.
  • the contact angle with water of the resin coating layer located on the outer surface side of the container after the molding process is in the range of 82 ° to 100 ° after the molding process.
  • a biaxially stretched film is used to form a resin-coated layer, and the film is heat-sealed on both sides of a metal plate heated to the melting point of the resin or higher. It is characterized by. It is more preferable that the heating temperature of the metal plate is (melting point of resin + 50 ° C.) or less.
  • the metal container according to the present invention is a metal container formed by molding the resin-coated metal plate according to the present invention, and the contact angle with water of the resin film layer located on the outer surface side of the metal container is 82. It is in the range of not less than 100 ° and not more than 100 °.
  • the molding flaw and the residual stress of the resin film layer located on the outer surface side of the container can be reduced after the molding process. It is possible to suppress appearance defects from occurring due to the heat treatment.
  • FIG. 1 is a cross-sectional view showing a configuration of a resin-coated metal plate according to an embodiment of the present invention.
  • FIG. 1 is a cross-sectional view showing a configuration of a resin-coated metal plate according to an embodiment of the present invention.
  • a resin coated metal plate 1 according to an embodiment of the present invention includes a metal plate 2, a resin coated layer 3 formed on one surface side of the metal plate 2, and the other of the metal plate 2. And a resin coating layer 4 formed on the surface side.
  • the resin coating layer 3 and the resin coating layer 4 are respectively positioned on the outer surface side and the inner surface side of the metal container after the molding process.
  • the metal plate 2 is formed of a steel plate such as tinplate or tin-free steel.
  • tinplate one having a tin plating amount of 0.5 to 15 g / m 2 is preferably used.
  • Tin-free steel a metal layer of chromium coating weight 50 ⁇ 200 mg / m 2, may deposition amount of chromium metal converted to its upper layer and a 3-chromium oxide layer of 30 mg / m 2.
  • the type of steel plate is not particularly limited as long as it can be formed into a desired shape, but the following components and manufacturing methods are preferable.
  • DR Double Reduced
  • IF Interstitial Free
  • the mechanical properties of the steel sheet are not particularly limited as long as they can be formed into a desired shape, but the yield strength YP is about 220 MPa or more and 580 MPa or less in order to maintain sufficient can body strength without impairing workability. It is desirable to use one. It is desirable that Rankford (r value), which is an index of plastic anisotropy, is 0.8 or more, and the in-plane anisotropy ⁇ r of r value has an absolute value of 0.7 or less. desirable.
  • the plate thickness of the steel plate can be set as appropriate from the shape of the target can and the required strength of the can. From the viewpoint of suppressing an increase in the cost of the steel sheet itself and the can body, it is desirable to use a sheet having a thickness of about 0.15 to 0.4 mm.
  • the component of steel for achieving said characteristic is not specifically limited, For example, what is necessary is just to contain components, such as Si, Mn, P, S, Al, N, and the content of Si is Within 0.001 to 0.1%, Mn content within 0.01 to 0.6%, P content within 0.002 to 0.05%, S content Is in the range of 0.002 to 0.05%, the Al content is in the range of 0.005 to 0.100%, and the N content is in the range of 0.0005 to 0.020%. preferable.
  • other components such as B, Cu, Ni, Cr, Mo, and V, may be contained, the content of these other components is 0.02% or less in total from the viewpoint of ensuring corrosion resistance and the like. It is desirable to be.
  • the resin coating layer 3 is formed of a resin material having an ethylene terephthalate unit of 97 mol% or more, preferably 98 mol% or more.
  • the resin is softened by heat generated by sliding with the tool during molding, so that molding flaws are likely to occur and surface irregularities after heat treatment are likely to occur.
  • the resin coating layer 3 may be a single layer or a structure of two or more layers, but the resin in each layer is such that the ethylene terephthalate unit is 97 mol% or more.
  • the resin coating layer 4 Since the resin coating layer 4 is bonded to both surfaces of the resin coating layer 3 and the metal plate 2, it is easy to manufacture when melted at a temperature close to the resin of the resin coating layer 3, and therefore the melting point equivalent to the resin of the resin coating layer 3 It is preferable that the ethylene terephthalate unit is 97 mol% or more.
  • the resin coating layer 4 may also be a single layer or a structure having two or more layers, but the resin in each layer preferably has 97 mol% or more of ethylene terephthalate units.
  • the resin in the resin coating layers 3 and 4 may be copolymerized with other dicarboxylic acid components and glycol components as long as the heat resistance and workability are not impaired.
  • the resin coating layer 3 it shall be in the range of less than 3 mol% in resin.
  • the resin film layer 4 it is preferable to set it in the range of less than 3 mol% in resin.
  • dicarboxylic acid component examples include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodium sulfoisophthalic acid, aromatic dicarboxylic acid such as phthalic acid, oxalic acid, succinic acid, Examples thereof include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dimer acid, maleic acid and fumaric acid, alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and oxycarboxylic acids such as p-oxybenzoic acid.
  • glycol components include aliphatic glycols such as propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol, alicyclic glycols such as cyclohexanedimethanol, aromatic glycols such as bisphenol A and bisphenol S, and diethylene glycol. It can be illustrated. These dicarboxylic acid components and glycol components may be used in combination of two or more.
  • the resin material for forming the resin coating layers 3 and 4 is not limited by the manufacturing method.
  • a resin material can be formed by utilizing a method in which a copolymer component is subjected to a transesterification reaction and then a reaction product obtained is subjected to a polycondensation reaction to obtain a copolymer polyester.
  • ethylene terephthalate resin and butylene terephthalate resin may be mixed to form a resin material.
  • additives such as a fluorescent brightener, an antioxidant, a heat stabilizer, an ultraviolet absorber, and an antistatic agent may be added as necessary. Addition of a fluorescent brightening agent is effective for improving the whiteness. It is preferable to use a biaxially stretched film produced by melt-extruding a resin having such a composition from a T-die and forming it into a thin film and then stretching it in the longitudinal and transverse directions.
  • the pressurizing pressure at the time of coating is not particularly limited, but the surface pressure is preferably in the range of 9.8 to 294 N (1 to 30 kgf / cm 2 ).
  • the surface pressure is smaller than this range, even if the temperature at the interface between the metal plate 2 and the resin coating layers 3 and 4 is equal to or higher than the melting point, the time for which the temperature is equal to or higher than the melting point is short, the resin coating layer The melting of 3 and 4 becomes insufficient, and sufficient adhesion between the resin coating layers 3 and 4 and the metal plate 2 may not be obtained.
  • the surface pressure is larger than this range, the resin coating layers 3 and 4 may melt and adhere to the roll.
  • the resin coating layer 3 on the outer surface side of the container has a difference between the heat of crystallization and the heat of fusion after coating on the metal plate 2 of 1 J / g or more and 20 J / g or less, preferably 1 J / g in terms of unit weight. g or more and 15 J / g or less, more preferably 3 J / g or more and 10 J / g or less.
  • the heat of crystallization and the heat of fusion can be measured using a differential scanning calorimeter (Differential Scanning Calorimetry: DSC).
  • DSC differential Scanning Calorimetry
  • the difference between the amount of heat of crystallization and the amount of heat of fusion of the resin coating layer 3 is less than 1 J / g, the residual stress after molding is reduced, but the impact resistance is reduced, and when a certain level of impact is applied, Resin film cracking occurs.
  • the difference between the amount of heat of crystallization and the amount of heat of fusion is greater than 20 J / g, the degree of crystallinity of the resin coating layer 3 is increased, and the residual stress after molding is increased. Will occur. From the above, the difference between the heat of crystallization and the heat of fusion of the resin coating layer 3 on the outer surface side of the container is 1 J / g or more and 20 J / g or less.
  • the resin coating layer 4 on the inner surface side of the container has a difference between the heat of crystallization and the heat of fusion after being coated on the metal plate 2 in the range of 1 J / g or more and 20 J / g or less in terms of unit weight. It is desirable that it be formed of a resin material. When the difference between the amount of heat of crystallization and the amount of heat of fusion is less than 1 J / g, the impact resistance after the molding process decreases, and when an impact of a certain level or more is applied, a resin film crack may occur.
  • the degree of crystallinity of the resin coating layers 3 and 4 is the orientation degree and melting point of the resin coating layers 3 and 4 before coating, and coating conditions (steel plate heating temperature, surface pressure during coating, time to cooling after coating, after coating Can be controlled by adjusting the cooling temperature and the line speed.
  • the crystallinity of the resin coating layers 3 and 4 can be lowered by increasing the heating temperature of the metal plate 2 during coating.
  • the heating temperature of the metal plate 2 is higher than the melting point of the resin coating layers 3 and 4, but is preferably about 10 to 50 ° C.
  • the crystallinity degree of the resin film layers 3 and 4 can be made low by reducing a surface pressure and making the cooling effect of the resin film layers 3 and 4 by the pressurization at the time of covering small.
  • the crystallization degree of the resin coating layers 3 and 4 is reduced by shortening the time until the cooling starts after coating and suppressing the crystallization of the resin coating layers 3 and 4 in the cooling process after coating. Can do.
  • the time until the start of cooling after coating is in the range of 0.5 to 10 seconds, depending on the length of the line and the line speed.
  • the crystallinity of the resin coating layers 3 and 4 can be lowered even under the same heating temperature. This is because the influence of cooling or the like from heating to coating is reduced.
  • the melting point of the resin coating layer 3 is in the range of 250 ° C. or more and 265 ° C. or less.
  • the melting point difference between the layers is preferably 10 ° C. or less. More preferably, it is 6 ° C. or less, and further preferably 3 ° C. or less.
  • the melting point of the resin coating layer 3 is less than 250 ° C., the resin coating layer 3 is easily softened due to surface sliding during processing, processing heat generated by the metal plate 2, etc., and molding scratches are generated on the surface of the resin coating layer 3. Or may lead to resin breakage.
  • the melting point of the resin coating layer 3 is higher than 265 ° C.
  • the crystallinity of the resin coating layer 3 is high, and there is a possibility that the processing with a high degree of processing cannot be followed.
  • the difference in melting point of each layer is larger than 10 ° C., the melting state of each layer by heat treatment is greatly different, so that defects in appearance are likely to occur due to non-uniform displacement (flow).
  • the melting point of the resin coating layer 4 is also in the range of 250 ° C. or more and 265 ° C. or less from the viewpoint of bonding with the resin coating layer 3, and when the resin coating layer 4 has a structure of two or more layers,
  • the melting point difference between the resin coating layer 3 and the resin is desirably 10 ° C. or less, more desirably 6 ° C. or less, and further desirably 3 ° C. or less.
  • the melting point difference between each layer and the resin coating layer 3 is greater than 10 ° C., the melting state of each layer and the resin coating layer 3 due to the heat treatment is greatly different, so that defects are likely to occur due to non-uniform displacement (flow). Become.
  • a wax component is added to the resin coating layer 3 in order to suppress the occurrence of molding flaws in the resin coating layer 3 when a molding process with a high degree of processing is performed.
  • the wax component to be added is not particularly limited, but an organic lubricant is preferable, and fatty acids such as stearic acid, stearic acid ester, palmitic acid, palmitic acid ester, fatty acid ester, paraffin, polyethylene, etc., which have good compatibility with the polyester resin.
  • chain aliphatics can be used, it is particularly desirable to use carnauba wax having good compatibility with the polyester resin and a high melting point.
  • the amount of wax component added is in the range of 0.05 PHR to 5 PHR.
  • the added amount of the wax component is less than 0.05 PHR, the effect of lubrication is small, and the effect of suppressing appearance defects due to molding flaws cannot be obtained.
  • the added amount of the wax component is more than 5 PHR, there is a problem that the transfer of the wax component occurs when the resin coating layer 3 is wound in a roll shape, and the printability may be deteriorated.
  • the amount of the wax component added is preferably in the range of 0.10 PHR to 3 PHR, more preferably in the range of 0.20 PHR to 2 PHR.
  • the wax component tends to precipitate on the surface and the slidability tends to improve.
  • the added amount of the wax component is 0.05 PHR to 5 PHR
  • the position of the wax component in the thickness direction of the resin coating layer 3 is not limited, but it is added to the outermost surface layer of the resin coating layer 3.
  • the outermost surface layer is preferably 1 ⁇ m or more and 5 ⁇ m or less from the outermost surface.
  • the wax component of the outermost surface layer has a high effect of improving the slidability, and when added to the outermost surface layer, the effect of improving the slidability is enhanced even if the addition amount of the wax component is small.
  • the lowest layer of the resin film layer 3 it is preferable to add to the lowest layer of the resin film layer 3, and it is preferable that the lowest layer in that case is 1 micrometer or more and 5 micrometers or less from the lowest surface.
  • the lowermost wax component has an effect of improving the resin adhesion at the time of molding by relaxing the stress generated at the interface between the resin layer and the metal plate during processing.
  • the film thickness of the outermost surface layer and the lowermost layer to which the wax component is added is smaller than 1 ⁇ m, the molding damage of the resin coating layer 3 may not be sufficiently suppressed or the resin adhesion during molding may be inferior. In some cases, the gloss of the surface of the resin coating layer 3 cannot be sufficiently secured.
  • the film thickness of the outermost surface layer and the lowermost layer to which the wax component is added may be larger than 5 ⁇ m. However, since the improvement effect is further reduced, it is preferably 5 ⁇ m or less.
  • the contact angle with water of the resin film layer 3 located on the outer surface side of the metal container is in the range of 82 ° to 100 °. Preferably, it is more preferably in the range of 85 ° to 95 °.
  • the wax component is often present in the initially added layer, but in the container molding process, the resin film layer 3 is When a thermal history is received by molding or painting baking, the wax component tends to precipitate on the surface and improve the slidability.
  • the resin film layer 3 located on the outer surface side of the metal container and the water
  • the contact angle is in the range of 82 ° to 100 °, indicating that suitable molding has been performed.
  • the conditions of the heat history are not particularly limited, but it is preferable to hold at a temperature of melting point ⁇ 50 ° C. or higher and melting point + 30 ° C. or lower for 30 seconds or longer.
  • the contact angle with water after heating to reach 240 ° C. in 90 seconds and forcibly cooling with cold air is a resin located on the outer surface side of the molded container It was confirmed that there was a good correlation with the contact angle of the coating layer 3 with water.
  • the optimum contact angle range with water is 27 to 33 mN / m in terms of the optimum surface free energy range.
  • a wax component may be added to the resin in the same manner as the resin coating layer 3.
  • the addition amount of the wax component is also preferably in the range of 0.05 PHR to 5 PHR.
  • the resin coating layer 3 may be required to be white so that a process for improving design properties such as a printing process is possible. Therefore, the resin coating layer 3 desirably contains titanium oxide within a range of 5 PHR to 30 PHR, preferably 10 PHR to 25 PHR, more preferably 12 PHR to 20 PHR. When the content of titanium oxide is less than 5 PHR, sufficient whiteness may not be ensured after processing. On the other hand, when the content of titanium oxide is more than 30 PHR, the adhesiveness and workability between the metal plate 2 and the resin coating layer 3 may become a problem when a forming process with a high workability is performed.
  • the amount of titanium oxide with respect to the resin amount of the entire resin coating layer 3 is in the range of 5 PHR to 30 PHR, and the film thickness is 10 ⁇ m or more. Further, when the amount of titanium oxide in the vicinity of the outermost surface is high, it is easy to detach from the surface after molding. Therefore, the amount of titanium oxide at a position from the outermost surface of the resin coating layer 3 to at least 1 ⁇ m is preferably 2 PHR or less. . In addition, when the amount of titanium oxide in the vicinity of the lowermost surface is high, the adhesion with the base metal tends to be lowered. Therefore, the amount of titanium oxide in the range from the lowermost surface to at least 1 ⁇ m is more preferably 2 PHR or less.
  • the titanium oxide added to the resin coating layer 3 is not particularly limited, but it is preferable to use a rutile-type titanium oxide having a content of 90% or more. When the rutile type titanium oxide is lower than 90%, the dispersibility of the titanium oxide is not good when mixed with the resin material, and the molecular weight of the resin material may be lowered. In Examples and Comparative Examples of the present application, rutile type titanium oxide was used. As a method for adding titanium oxide, various methods as shown in the following (1) to (3) can be used. In addition, when adding titanium oxide using method (1), it is desirable to add titanium oxide to the reaction system as a slurry in which glycol is dispersed.
  • the thickness of the resin coating layer 3 to which titanium oxide is added is desirably in the range of 10 to 40 ⁇ m, preferably 12 to 35 ⁇ m, more preferably 15 to 25 ⁇ m in order to ensure the whiteness after processing. .
  • the thickness of the resin coating layer 3 is less than 10 ⁇ m, the resin coating layer 3 is easily cracked during processing.
  • the thickness of the resin coating layer 3 is larger than 40 ⁇ m, the residual stress due to molding becomes too large and the adhesion may be inferior.
  • the surface of the titanium oxide in order to improve the adhesion between the titanium oxide and the film resin, it is preferable to treat the surface of the titanium oxide with silica, alumina or the like.
  • the resin coating layers 3 and 4 may be a single layer having the same composition or a multilayer structure. Further, the resin coating layers 3 and 4 are preferably in the range of 10 ⁇ m or more and 40 ⁇ m or less in the case of a single layer or multiple layers. If it is less than 10 ⁇ m, the resin coating layer 3 may be cracked during processing and the coverage may be inferior, and if it exceeds 40 ⁇ m, the residual stress due to molding becomes too large and the adhesion may be inferior. In addition, as long as the resin coating layers 3 and 4 have a predetermined configuration, the layer forming method is not limited.
  • a plurality of films having different components may be laminated, or a plurality of components may be formed on the film by a melt extrusion method.
  • the thickness of each layer is preferably 1 ⁇ m or more from the viewpoint of adhesion and the like.
  • a film-like resin coating layer produced by a biaxial stretching method using a nip roll is thermocompression bonded to the metal plate, Subsequently, the resin film layer was coat
  • a resin coating layer (outer surface resin layer) with and without titanium oxide is positioned on the inner surface side of the container after molding processing. The other surface side of the metal plate was coated with a resin coating layer (inner surface resin layer) not containing titanium oxide.
  • the heat of crystallization was calculated from the area of the exothermic peak observed between 100 to 200 ° C.
  • the heat of fusion was calculated from the area of the endothermic peak observed between 200 ° C. and 280 ° C.
  • the amount of crystallization heat and the amount of heat of fusion per unit weight of the resin were calculated using the weight excluding the titanium oxide content as the amount of resin.
  • the whiteness of the resin coating layer 3 of the resin-coated metal plate was evaluated by the method shown in JIS Z 8722.
  • the measurement area was 30 mm ⁇
  • the measurement light source was the C condition
  • the L value of the Hunter Lab value measured under the observation condition of the 2 ° visual field with respect to the measurement light source was defined as whiteness.
  • L value is 75 or more, it is suitable as a white film.
  • the outer surface resin layer has an ethylene terephthalate unit of 97 mol% or more and a wax component in the range of 0.05 PHR to 5 PHR.
  • the difference between the amount of heat of crystallization and the amount of heat of fusion after being coated on the metal plate is formed of a resin material of 1 J / g or more and 20 J / g or less in terms of unit weight.
  • either the resin composition, the wax component, or the difference between the heat of crystallization and the heat of fusion of the outer surface resin layer is different.
  • the outer surface resin layer is formed of a resin material having a difference between the amount of heat of crystallization and the amount of heat of fusion of 0 J / g in terms of unit weight.
  • Score “ ⁇ ” When a film molding flaw occurs at a height within 1 mm from the can flange. Score “ ⁇ ”: When a film molding flaw occurs at a height position within 3 mm exceeding 1 mm from the can flange portion. Score “ ⁇ ”: When a film forming defect occurs at a height position exceeding 3 mm and within 5 mm from the can flange portion. Score “ ⁇ ”: When a film molding flaw occurs at a height position of more than 5 mm and within 10 mm from the can flange portion. Score “X”: When a film molding flaw occurs up to a height position exceeding 10 mm from the can flange portion.
  • Score “ ⁇ ” When a surface irregularity defect occurs at a height position within 2 mm exceeding 1 mm from the can flange portion. Score “ ⁇ ”: When a surface irregularity defect occurs at a height of 3 mm or more exceeding 2 mm from the can flange portion. Rating “ ⁇ ”: When a surface irregularity defect occurs at a height position within 3 mm exceeding 3 mm from the can flange portion. Score “X”: When a surface irregularity defect occurs at a height position exceeding 5 mm from the can flange portion.
  • a sample for peel test (width 15 mm ⁇ length 120 mm) was cut out from the can body of the deep-drawn can formed in the appearance evaluation.
  • the resin film layer on the outer surface of the can is partly peeled off from the long side end of the cut sample, and the peeled resin film layer is opened in the direction opposite to the metal plate from which the resin film layer has been peeled (angle: 180 degrees).
  • a peel test was conducted at a tensile speed of 30 mm / min, and the adhesion per 15 mm width was evaluated according to the following criteria.
  • T3CA JIS G 3303
  • TFS Tin Free Steel, metal Cr layer: 120 mg / m 2
  • Cr oxide layer 10 mg / m 2 in terms of metal Cr
  • film heat Resin coating layers of Examples 101 to 141 and Comparative Examples 101 to 112 shown in Tables 3A to 3D below were formed on both surfaces of a metal plate by using a pressure bonding method.
  • two or three resin coating layers shown in Tables 3A to 3D are laminated as a film, and the metal plate is the melting point of the resin coating layer (if each layer has a different melting point, the melting point of the highest layer is used).
  • a film-like resin coating layer produced by a biaxial stretching method using a nip roll is thermocompression bonded to a metal plate, and then cooled by water cooling within 5 seconds, The resin film layer was coat
  • a resin coating layer (outer surface resin layer) with and without titanium oxide is positioned on the inner surface side of the container after molding processing. The other surface side of the metal plate was coated with a resin coating layer (inner surface resin layer) not containing titanium oxide.
  • the outer surface resin layer has a structure of two or more layers, and the film thickness of the outermost surface layer is 1 ⁇ m or more.
  • Each of the resin coating layers is 97 mol% or more of ethylene terephthalate unit
  • the outermost surface layer contains a wax component in the range of 0.05 PHR or more and 5 PHR or less, and the amount of the wax component is based on the resin amount of the entire resin coating When converted, it is 0.05 PHR or more and 5 PHR or less
  • the difference between the heat of crystallization and the heat of fusion of the resin coating layer after being coated on the metal plate is a range of 1 J / g or more and 20 J / g or less in terms of unit weight.
  • the outer resin layer is formed of a resin material having a difference between the amount of crystallization heat and the heat of fusion converted to 0 J / g per unit weight.
  • a resin film layer formed on the both sides of the metal plate is obtained by thermocompression bonding the film-like resin film layer produced by the biaxial stretching method using a nip roll to a metal plate and then cooling with water cooling within 5 seconds.
  • a resin coating layer (outer surface resin layer) with or without titanium oxide was coated on the back surface side.
  • the outer resin layer has a three-layer structure including an outermost surface layer, an intermediate layer, and a lowermost layer.
  • Each of the coating layers has an ethylene terephthalate unit of 97 mol% or more, has a layer containing a wax component of 1 ⁇ m or more and 5 ⁇ m or less from the outermost surface and the lowermost surface, respectively, and the amount of wax relative to the amount of resin in the layer containing wax
  • the amount of wax relative to the amount of resin in the entire resin coating layer is in the range of 0.05 PHR to 5 PHR, and the difference between the heat of crystallization and the heat of fusion of the resin coating layer after being coated on the metal plate is per unit weight.
  • the resin material is in the range of 1 J / g or more and 20 J / g or less.
  • either the resin composition, the wax component, or the difference between the heat amount of crystallization and the heat of fusion of the outer surface resin layer is different, and the resin film of Comparative Example 211 is used.
  • the outer surface resin layer is formed of a resin material having a difference between the amount of heat of crystallization and the amount of heat of fusion of 0 J / g in terms of unit weight.
  • the present invention it is possible to provide a resin-coated metal plate, a method for producing a resin-coated metal plate, and a metal container that can suppress appearance defects due to molding and heat treatment.

Landscapes

  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

La présente invention concerne une plaque métallique revêtue de résine qui est pourvue d'une couche de revêtement de résine sur les deux surfaces d'une plaque métallique, et qui est caractérisée en ce qu'une couche de revêtement de résine, qui est positionnée sur le côté de surface externe d'un récipient après mise en forme, est formée d'un matériau de résine comprenant un motif téréphtalate d'éthylène dont la teneur est supérieure ou égale à 96 % en moles et contenant un constituant de type cire dont la teneur est située dans la plage allant de 0,05 PHR à 5 PHR (inclus), tout en présentant une différence entre l'enthalpie de cristallisation et l'enthalpie de fusion située dans la plage allant de 1 J/g à 20 J/g (inclus) par poids unitaire après avoir été disposé sur la plaque métallique.
PCT/JP2015/085028 2015-02-27 2015-12-15 Plaque métallique revêtue de résine, procédé de production d'une plaque métallique revêtue de résine, et récipient métallique WO2016136099A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11072149B2 (en) * 2017-12-15 2021-07-27 Toyobo Co., Ltd. Biaxially drawn colored polyester film for laminating metal sheet
JPWO2021182256A1 (fr) * 2020-03-11 2021-09-16

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001220453A (ja) * 1999-12-03 2001-08-14 Toray Ind Inc 成形加工用二軸延伸ポリエステルフィルム
JP2002264258A (ja) * 2001-03-14 2002-09-18 Nkk Corp 容器用フィルムラミネート金属板
JP2004168365A (ja) * 2002-11-20 2004-06-17 Nippon Steel Corp 容器用金属板およびその製造方法
WO2013030972A1 (fr) * 2011-08-31 2013-03-07 Ｊｆｅスチール株式会社 Tôle métallique revêtue de résine
JP2014008739A (ja) * 2012-07-02 2014-01-20 Jfe Steel Corp 樹脂被膜金属板
JP2014144576A (ja) * 2013-01-29 2014-08-14 Jfe Steel Corp 樹脂被膜金属板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001220453A (ja) * 1999-12-03 2001-08-14 Toray Ind Inc 成形加工用二軸延伸ポリエステルフィルム
JP2002264258A (ja) * 2001-03-14 2002-09-18 Nkk Corp 容器用フィルムラミネート金属板
JP2004168365A (ja) * 2002-11-20 2004-06-17 Nippon Steel Corp 容器用金属板およびその製造方法
WO2013030972A1 (fr) * 2011-08-31 2013-03-07 Ｊｆｅスチール株式会社 Tôle métallique revêtue de résine
JP2014008739A (ja) * 2012-07-02 2014-01-20 Jfe Steel Corp 樹脂被膜金属板
JP2014144576A (ja) * 2013-01-29 2014-08-14 Jfe Steel Corp 樹脂被膜金属板

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11072149B2 (en) * 2017-12-15 2021-07-27 Toyobo Co., Ltd. Biaxially drawn colored polyester film for laminating metal sheet
JPWO2021182256A1 (fr) * 2020-03-11 2021-09-16
WO2021182256A1 (fr) * 2020-03-11 2021-09-16 Ｊｆｅスチール株式会社 Plaque métallique revêtue de résine pour récipients
CN115210071A (zh) * 2020-03-11 2022-10-18 杰富意钢铁株式会社 容器用树脂被覆金属板
JP7226555B2 (ja) 2020-03-11 2023-02-21 Ｊｆｅスチール株式会社 容器用樹脂被覆金属板

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