WO2015068720A1 - Feuille métallique revêtue de résine et boîte sans raccord - Google Patents

Feuille métallique revêtue de résine et boîte sans raccord Download PDF

Info

Publication number
WO2015068720A1
WO2015068720A1 PCT/JP2014/079316 JP2014079316W WO2015068720A1 WO 2015068720 A1 WO2015068720 A1 WO 2015068720A1 JP 2014079316 W JP2014079316 W JP 2014079316W WO 2015068720 A1 WO2015068720 A1 WO 2015068720A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
metal plate
resin coating
polyester resin
layer
Prior art date
Application number
PCT/JP2014/079316
Other languages
English (en)
Japanese (ja)
Inventor
雅志 池渕
宗光 弘津
神崎　敬三
修平 廣森
正幸 内田
智靖 武永
昌巳 末永
康介 佐々木
Original Assignee
東洋製罐株式会社
東洋鋼鈑株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋製罐株式会社, 東洋鋼鈑株式会社 filed Critical 東洋製罐株式会社
Publication of WO2015068720A1 publication Critical patent/WO2015068720A1/fr

Links

Images

Classifications

    • 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

Definitions

  • the present invention relates to a resin-coated metal plate in which a polyester resin coating is formed on the surface of the metal plate. More specifically, when forming into a seamless can, the metal exposure occurrence rate on the inner surface of the can is low, and The present invention relates to a resin-coated metal plate capable of effectively suppressing corrosion.
  • tinplate tin free steel (TFS), aluminum alloy, etc.
  • TFS tin free steel
  • aluminum alloy etc.
  • Such a metal plate is generally provided with a resin coating for the purpose of preventing corrosion due to the influence of the contents.
  • Patent Document 1 a homogenous polyethylene terephthalate film is used as a synthetic resin film when a synthetic steel film is continuously pressed onto a surface of a heated steel plate with a laminating roll to produce a laminated steel plate.
  • a method for producing a polyethylene terephthalate (PET) coated steel sheet is disclosed wherein the temperature is within the resin melting point ⁇ 20 ° C., the nip length of the laminate roll is 40 to 80 mm, and the surface temperature of the laminate roll is 120 ° C. or higher.
  • PET-coated steel sheet is provided in which the occurrence of bubble defects in the film is prevented while maintaining film performance (adhesion and scratch resistance).
  • the PET-coated steel sheet obtained by the method of Patent Document 1 has a residual coated crystal amount of PET coating measured by X-ray diffraction of 400 cps or more, and thus a resin-coated steel sheet having such a high orientation is used.
  • a resin-coated steel sheet having such a high orientation is used.
  • Patent Document 2 a resin-coated metal plate having two unoriented layers on the surface of the metal plate on the inner surface side of the can.
  • This resin-coated metal plate is produced by thermally laminating an unstretched film (cast film) on the metal plate, or by extrusion lamination in which a molten resin is directly supplied onto the metal plate.
  • the resin coating is formed by thermal lamination of an unstretched film, the unstretched film has a problem that it is easily broken during lamination and has poor handleability, and is inferior in productivity as compared to a stretched film.
  • the object of the present invention is excellent in formability even when subjected to severe forming methods such as drawing ironing, low metal exposure rate on the inner surface of the can, and effectively suppressing corrosion at the tightening portion. And providing a resin-coated metal sheet. Another object of the present invention is to provide a resin-coated metal plate excellent in productivity and economy.
  • the inventors of the present invention relate to an ethylene terephthalate polyester resin, and when the biaxial orientation degree of the resin after coating on a metal plate is lower than 8.0 cps / ⁇ m.
  • the metal exposure rate is suppressed to a very low value of less than 1%, but if it exceeds 8.0 cps / ⁇ m, the metal exposure rate is rapidly increased.
  • the present invention has been completed (see FIG. 1).
  • FIG. 1 In FIG.
  • the polyester resin is an ethylene terephthalate-based polyester resin, and the (100) surface of the polyester resin coating
  • the biaxial orientation degree expressed by the value obtained by dividing the highest peak intensity in the range of the X-ray diffraction angle 2 ⁇ of 23 to 29 ° by the thickness of the polyester resin coating is in the range of 3.0 to 8.0 cps / ⁇ m.
  • the polyester resin coating comprises a single-layer resin film of an ethylene terephthalate-based polyester resin, and the single-layer resin film contains isophthalic acid as a copolymerization component in an amount of 2 to 15 mol%, Have an intrinsic viscosity of ⁇ 1.0 dL / g, (2)
  • the polyester resin coating is formed by laminating a biaxially stretched polyester resin film on a metal plate under the condition that the temperature of the metal plate is Tm + 25 to Tm + 45 ° C. ⁇ Tm: melting point of the polyester resin (° C.) ⁇ .
  • the polyester resin coating is formed on a metal plate via a primer, (4)
  • the metal plate is tin-free steel, Is preferred.
  • a two-layer colored resin film including a surface layer and a lower layer is laminated on the surface opposite to the surface on which the polyester resin coating is provided of the metal plate so that the lower layer is in contact with the metal plate.
  • the surface layer and the lower layer are formed using a copolyester resin or a blend of a copolyester resin and a homopolyester resin, and the surface layer has an intrinsic viscosity of 0.66 to 0.90 dL / g,
  • the melting point is 215 to 230 ° C.
  • the content of the color pigment is 20% by weight or less
  • the lower layer has an intrinsic viscosity of 0.46 to 0.85 dL / g, the melting point of 235 to 250 ° C.
  • the color pigment Is more than the surface layer and not more than 50% by weight, or (6)
  • a three-layer colored resin film including a surface layer, an intermediate layer and a lower layer on the surface of the metal plate opposite to the surface on which the polyester resin coating is provided, so that the lower layer is in contact with the metal plate
  • the surface layer, the intermediate layer, and the lower layer are formed using a copolyester resin or a blend of a copolyester resin and a homopolyes
  • the intermediate layer has an intrinsic viscosity of 0.46 to 0.85 dL / g and melting point of 235 to 250 ° C.
  • the content of the color pigment is more than that of the other layers and not more than 50% by weight
  • the lower layer has an intrinsic viscosity of 0.66 to 0.90 dL / g, a melting point of 215 to 230 ° C., and Colored pigment
  • the content is 20 wt% or less, Is preferred.
  • a seamless can formed by drawing and ironing, drawing, drawing, stretching, or drawing and ironing the resin-coated metal plate so that the polyester resin coating is on the inner surface of the can. Is done.
  • the biaxial orientation degree of the polyester resin after coating on the metal plate is adjusted to a specific range of 3.0 to 8.0 cps / ⁇ m.
  • the metal exposure rate on the inner surface side of the can is greatly reduced. That is, side seamless cans widely used as beverage cans (side seamless cans) are formed, for example, by subjecting a resin-coated metal plate to drawing and ironing, but if the orientation of the resin is high, ironing In the process, a part of the resin covering the inner surface of the can is cracked and the metal part is exposed. In particular, the probability of exposure at the boundary of 8.0 cps / ⁇ m increases rapidly. Since the degree is set lower than the boundary value, the metal exposure occurrence rate is effectively suppressed.
  • the orientation of the resin coating is low, the randomness of the molecules is high, and there is a large room for further orientation of the molecules in the resin in the height direction of the can, so that the resin coating can be applied at a desired magnification without causing cracks. Can extend.
  • the orientation of the resin coating is high, molecules that can be further oriented do not remain in the resin coating, and the resin coating is cracked. That is, how much the resin coating can be extended in the ironing process depends on how many molecules that do not contribute to the orientation remain before the ironing process, and the residual amount of non-oriented molecules is the resin. If there is not enough to extend the coating, it is considered that the processing limit is reached and the probability of cracking suddenly increases.
  • the resin-coated metal plate of the present invention has a certain degree of biaxial orientation held in the resin after coating, the resin-coated metal plate has excellent corrosion resistance in the tightening portion of the seamless can made of this resin-coated metal plate.
  • the body hook radius represented by a in FIG. 2
  • the pressure ridge represented by b in FIG. 2
  • the load is locally applied to the part. More specifically, stress due to bending is applied to the body hook radius, and stress is applied to the pressure ridge perpendicular to the surface direction.
  • the resin coating according to the present invention does not have such a concern because it has sufficient orientation to obtain good winding portion corrosion resistance.
  • the resin-coated metal plate of the present invention is produced from a stretched film rather than an unstretched film, the problems of film handling at the time of production and productivity of the film itself are eliminated, which is extremely advantageous industrially. is there.
  • the rate of metal exposure refers to the proportion of the can produced by metal exposure on the inner surface of the can body and the bottom of the can before occupying the cover. This is an index to be evaluated. Specifically, when a can is filled with a predetermined electrolyte and energized, a can that has a current of 0.5 mA or more flows as a metal exposure generating can. Determining the percentage (%) of generated cans.
  • Metal plate In the present invention, various surface-treated steel plates and light metal plates such as aluminum are used as the metal plate.
  • surface-treated steel sheets cold-rolled steel sheets are subjected to temper rolling or secondary cold rolling after annealing, and surface treatment such as galvanization, tin plating, nickel plating, electrolytic chromic acid treatment, chromic acid treatment, zirconium compound treatment, etc. What performed 1 type, or 2 or more types can be used.
  • an electrolytic chromic acid-treated steel plate ⁇ tin-free steel (hereinafter referred to as “TFS”) ⁇ can be particularly preferably used from the viewpoint of coating film adhesion and corrosion resistance.
  • the TFS preferably comprises a metal chromium layer of 10 to 200 mg / m 2 and a chromium hydrated oxide layer of 1 to 50 mg / m 2 (as chromium).
  • a metal chromium layer of 10 to 200 mg / m 2 and a chromium hydrated oxide layer of 1 to 50 mg / m 2 (as chromium).
  • Another example of the surface-treated steel sheet is a tin plate having a tin plating amount of 0.5 to 11.2 g / m 2 .
  • This tin plate is preferably subjected to chromic acid treatment, sodium dichromate treatment or phosphoric acid chromic acid treatment so that the chromium content is 1 to 30 mg / m 2 .
  • Still another example is an aluminum-coated steel sheet subjected to aluminum plating, aluminum pressure welding, or the like.
  • an aluminum alloy plate is used in addition to a so-called aluminum plate.
  • the aluminum alloy plate excellent in corrosion resistance and workability is Mn: 0.2 to 1.5% by weight, Mg: 0.8 to 5% by weight, Zn: 0.25 to 0.3% by weight, And Cu: 0.15 to 0.25% by weight, with the balance being Al.
  • These light metal plates are also preferably subjected to chromic acid treatment, chromic acid chromic acid treatment, zirconium compound treatment or the like so that the chromium amount becomes 20 to 300 mg / m 2 in terms of metal chrome.
  • the base plate thickness of the metal plate varies depending on the type of metal, the use or size of the container, but generally it is preferably 0.10 to 0.50 mm. Of these, in the case of a surface-treated steel plate, a thickness of 0.10 to 0.30 mm is preferable from the viewpoint of the strength and formability of the seamless can obtained, and in the case of a light metal plate, 0.15 to 0.40 mm. Is preferable.
  • a polyester resin specifically, ethylene terephthalate is used as a resin (hereinafter also referred to as “inner surface resin”) to be coated on the inner surface of the metal plate.
  • ner surface resin an ethylene terephthalate-based polyester resin containing units in an amount of 85 mol% or more is used.
  • the degree of biaxial orientation after coating of the polyester resin of the present invention is in the range of 3.0 to 8.0 cps / ⁇ m.
  • the degree of biaxial orientation is higher than the above range, since there are few non-oriented molecules in the polyester resin coating, the resin-coated metal plate is subjected to severe processing load during can making, for example, in the can height direction in ironing processing. The probability that the metal plate cannot be stretched and the metal plate is exposed is significantly increased.
  • polyester resin coating becomes hard, there is a problem that the adhesion between the metal plate and the resin coating is impaired.
  • degree of biaxial orientation is too low, when the can is molded, filled and wound, cracks occur in the resin coating at the tightening portion, and corrosion (PET floating) tends to occur in this portion.
  • the biaxial orientation degree is the highest peak intensity value (cps) among the peaks in the range where the X-ray diffraction angle 2 ⁇ of the (100) plane of the polyester resin coating is 23 to 29 °. It is expressed by a value (cps / ⁇ m) divided by ( ⁇ m).
  • X-ray diffraction is measured using, for example, an X-ray diffractometer ⁇ RINT2100, manufactured by Rigaku Corporation), using Cu as the target (Cu-K ⁇ ), a tube voltage of 40 kV, and a tube current of 40 mA.
  • the ethylene terephthalate-based polyester resin forming the inner surface resin coating film contains 2 to 15 mol% of isophthalic acid as a copolymerization component.
  • isophthalic acid since the orientation of the polyester resin is limited to a narrow range, the orientation must be strictly adjusted. Therefore, it is preferable to use isophthalic acid in the above range. When the amount of isophthalic acid is large, the orientation of the polyester resin coating tends to be low, and as a result, the resin coating becomes too soft, and cracks occur in the winding resin coating in the filling and lid winding process after can molding. It becomes easy.
  • the amount of isophthalic acid is less than the above range, the orientation of the polyester resin tends to be high, the flexibility of the resin coating is not imparted, and the resin coating tears in severe processes such as the ironing process of the can molding process. Metal exposure is likely to occur.
  • the polyester resin forming the inner resin coating film has an intrinsic viscosity (IV) measured using a phenol / tetrachloroethane mixed solvent as a solvent in the range of 0.5 to 1.0 dL / g. It is preferable to be in the range of 0.6 to 0.8 dL / g.
  • IV intrinsic viscosity
  • the intrinsic viscosity is larger than the above range, the adhesion between the polyester resin coating and the metal plate is deteriorated.
  • the intrinsic viscosity is smaller than the above range, a molecular weight sufficient to form a polyester resin film as a material cannot be secured.
  • the ethylene terephthalate-based polyester resin film may contain a small amount of other copolymer components.
  • carboxylic acid components other than isophthalic acid and terephthalic acid components include, but are not limited to, the following carboxylic acid components.
  • examples of alcohol components other than ethylene glycol include the following alcohol components.
  • the polyester resin film contains a film compounding agent known per se, for example, an antiblocking agent such as amorphous silica, a pigment such as titanium dioxide, an antistatic agent, an antioxidant, a lubricant and the like. Can be blended according to a known formulation.
  • a film compounding agent known per se for example, an antiblocking agent such as amorphous silica, a pigment such as titanium dioxide, an antistatic agent, an antioxidant, a lubricant and the like.
  • the inner surface resin coating can be formed from a multilayer film in which another layer is further provided on the polyester resin film having the above-mentioned characteristics. From the viewpoint of simplifying the plate manufacturing process, it is preferably formed from a single layer polyester resin film.
  • the layer structure of the inner surface resin coating is more complex, considerations for adhesion between layers and the like are necessary. However, such considerations are unnecessary if a single-layer resin film is used.
  • the above-described excellent moldability and corrosion resistance can be exhibited without problems even with an inner surface resin coating formed from a single layer resin film.
  • the inner surface resin coating has a multi-layer structure, the above-described various characteristics and compositions only have to be satisfied by the overall average value.
  • the thickness of the inner surface resin coating is preferably 10 to 40 ⁇ m, particularly preferably 17 to 30 ⁇ m after being coated on the metal plate. That is, if the inner surface resin coating is a single layer of only a polyester resin coating, the polyester resin coating has a thickness in the above range, and if it is a multilayer, the total thickness of the polyester resin coating and other layers combined is in the above range. It is preferable that it exists in. If it is thicker than the above range, the resin strength becomes too high, and the resin is liable to break during the winding process, and there is a possibility that corrosion (PET floating) may occur in the wound part. On the other hand, when the thickness is small, metal exposure tends to occur due to drawing ironing or the like.
  • an adhesion primer can be provided between the inner surface resin coating and the metal plate, whereby the adhesion of the resin coating can be further improved. Since it is technically difficult to previously provide the adhesive primer on the metal plate, it is provided on the resin film and thermally welded onto the metal plate. In the present invention, since a stretched resin film is used as a material, there is little deformation due to heat during primer application and drying, and it is easy to provide a primer in advance. When the primer is provided, the adhesion between the inner surface resin coating and the metal plate is improved, and there is no possibility that the metal is exposed or the contents enter between the metal portion and the inner surface resin coating after canning.
  • This resin-coated metal plate can be applied to cans for acidic beverages having strong corrosive properties such as fruit juice beverages.
  • primer paints excellent in adhesion and corrosion resistance conventionally known primers such as epoxy phenol primer paints and polyester phenol primer paints can be used, but bisphenol-free primer paints are used from the viewpoint of hygiene. It is preferable to use a polyester phenol primer coating comprising a polyester resin and a resol type phenol resin derived from m-cresol as a curing agent.
  • the adhesive primer layer is generally preferably provided with a thickness of 0.01 to 10 ⁇ m.
  • outer surface resin coating On the surface of the metal plate that is to be the outer surface side of the can, that is, on the surface of the metal plate opposite to the surface on which the inner surface resin coating is provided, it has been used for ordinary can coatings and resin coated metal plates.
  • this resin coating is referred to as an outer surface resin coating.
  • the resin film used for the outer surface resin coating may have a single-layer structure, but preferably has a multilayer structure such as a two-layer structure or a three-layer structure.
  • the resin film When the resin film has a two-layer structure including a surface layer and a lower layer, the resin film is used for lamination so that the lower layer is in contact with the metal plate.
  • the surface layer and the lower layer are preferably formed using a copolyester resin or a blend of a copolyester resin and a homopolyester resin. This is because the quality of the resin-coated metal plate can be easily controlled by using the same material for the outer resin coating film as that of the inner resin coating film.
  • PET / IA polyethylene terephthalate / isophthalate
  • PET / IA polyethylene terephthalate / isophthalate
  • the lower layer it is preferable to use a polyethylene terephthalate /
  • the intrinsic viscosity of the surface layer is preferably 0.66 to 0.90 dL / g from the viewpoint of mechanical strength.
  • the intrinsic viscosity of the lower layer is preferably 0.46 to 0.85 dL / g. This is because if the intrinsic viscosity of the lower layer is too large, the adhesion between the metal plate and the outer surface resin coating may be impaired. Moreover, it is because there exists a possibility that molecular weight sufficient for formation of a film cannot be ensured when the intrinsic viscosity of a lower layer is too small.
  • a coloring pigment such as titanium dioxide may be added to the surface layer and the lower layer from the decorative surface, and the resin film may be a two-layer colored resin film.
  • the content of the color pigment in the surface layer is 0 to 20% by weight, particularly 5 to 10% by weight, and the content of the color pigment in the lower layer is more than 50% by weight (zero In particular, it is preferably 20 to 40% by weight.
  • the melting point of the surface layer is preferably 215 to 230 ° C. from the viewpoint of preventing cracking during can molding.
  • the resin film used for forming the outer surface resin coating has a three-layer structure including a surface layer, an intermediate layer, and a lower layer
  • the resin film is used for lamination so that the lower layer is in contact with the metal plate.
  • the surface layer, intermediate layer and lower layer are preferably formed using a copolymerized polyester resin or a blend of a copolymerized polyester resin and a homopolyester resin.
  • a copolymerized polyester resin or a blend of a copolymerized polyester resin and a homopolyester resin for example, it is preferable to use a polyethylene terephthalate / isophthalate resin with an isophthalic acid content of 7 to 14 mol% from the viewpoint of printing ink adhesion and resin strength.
  • the intermediate layer it is preferable to use a polyethylene terephthalate / isophthalate resin having an isophthalic acid content of 2 to 5 mol% from the viewpoint of scraping the outer surface resin coating during molding.
  • the intrinsic viscosity of the surface layer is preferably 0.66 to 0.90 dL / g from the viewpoint of mechanical strength.
  • the intrinsic viscosity of the intermediate layer is preferably 0.46 to 0.85 dL / g from the viewpoint of ensuring adhesion with the metal plate.
  • the intrinsic viscosity of the lower layer is preferably 0.66 to 0.90 dL / g from the viewpoint of providing adhesion to the metal plate and securing a molecular weight sufficient for film formation.
  • the thickness ratio of the surface layer, the intermediate layer, and the lower layer is preferably in the range of 6 to 18 for the intermediate layer and in the range of 0.5 to 2 for the lower layer when the surface layer is 1.
  • a colored pigment such as titanium dioxide may be added to each layer, and the resin film may be a three-layer colored resin film.
  • the content of the color pigment is 0 to 20% by weight in the surface layer, particularly 0 to 10% by weight
  • the intermediate layer is 50% on the condition that it is higher than the other layers (surface layer and lower layer).
  • % Or less excluding zero
  • the lower layer is preferably 0 to 20% by weight, particularly 0 to 10% by weight.
  • the melting point of the surface layer is preferably 215 to 230 ° C. from the viewpoint of preventing cracking during can molding.
  • the melting point of the intermediate layer is 235 to 250 ° C. and the melting point of the lower layer is 215 to 230 ° C.
  • the thickness of the outer surface resin coating is preferably 1 to 20 ⁇ m, particularly 8 to 16 ⁇ m, after being coated on the metal plate. In the case of multiple layers, the total thickness may be in the above range.
  • the production method of the outer resin film can be either stretched or unstretched. However, using a stretched film eliminates the problems of film handling during production and the productivity of the film itself, and is extremely advantageous industrially. It is.
  • the resin-coated metal plate of the present invention can be produced by using a biaxially stretched polyester resin film as the inner surface resin coating film and thermally bonding the inner surface resin coating film and the outer surface resin coating film to the metal plate. it can.
  • the biaxial orientation degree of the biaxially stretched polyester resin film that is the material of the inner surface resin coating is set so that the value after finally coating the metal plate is in the above-mentioned range before the thermal bonding. Specifically, 20 to 150 cps / ⁇ m is preferable, and 50 to 130 cps / ⁇ m is particularly preferable. Since the present invention uses a polyester resin film that is not unstretched but biaxially stretched, it is advantageous in terms of the productivity of the material film and the handleability of the material film during the production of the resin-coated metal sheet of the present invention. .
  • the inner surface resin coating is preferably formed from a single-layer polyester resin film, but can also be formed from a multilayer polyester resin film depending on the application. Further, when a primer is provided between the inner surface resin coating and the metal plate, the primer is provided on the inner surface resin coating film and used for the manufacturing process described later.
  • the outer resin coating film used for the production of the resin-coated metal plate of the present invention a film obtained by a known material and method is used on condition that the characteristics and composition of the outer resin coating film are satisfied.
  • the inner surface resin coating film and the outer surface resin coating film are subjected to a manufacturing process.
  • the metal plate 1 is heated by the heating roll 2 to a temperature in the range of the melting point (Tm) +25 to the melting point (Tm) + 45 ° C. of the polyester resin forming the inner resin coating film, and the laminating rolls 3A, 3B. Supply in between.
  • the inner surface resin coating film 4A and the outer surface resin coating film 4B are unwound from the supply rolls 5A and 5B, respectively, and supplied in such a positional relationship that the metal plate 1 is sandwiched between the laminate rolls 3A and 3B.
  • the laminating roll 3A is kept constant at 50 to 110 ° C., and 3B is kept constant within the range of 60 to 100 ° C.
  • the inner surface resin coating film 4A and the outer surface resin coating film 4B are thermally bonded to both surfaces of the metal plate 1 at a plate passing speed of 130 to 230 m / min, respectively.
  • a water tank 12 containing cooling water for rapidly cooling the resin-coated metal plate 11 to be formed, and a guide roller 13 for guiding the resin-coated metal plate into the water tank. Has been placed.
  • the present invention it is necessary to provide an inner surface resin coating having a biaxial orientation degree (3.0 to 8.0 cps / ⁇ m) in a very limited range on the metal plate.
  • a biaxial orientation degree (3.0 to 8.0 cps / ⁇ m) in a very limited range on the metal plate.
  • the heating roll temperature, the laminate roll temperature, and the sheet passing speed within a certain range. For example, even if the laminating roll temperature and the sheet passing speed are set to appropriate values, if the heating roll temperature is too high or too low, the biaxial orientation degree varies within the resin coating, or the biaxial orientation degree is Out of range.
  • the seamless can of the present invention can be formed by adopting a method known per se for the resin-coated metal plate of the present invention thus prepared. That is, by punching out the resin-coated metal plate of the present invention, and then subjecting the inner surface resin coating to the inner surface of the can, it is subjected to seamless processing such as drawing ironing processing, drawing processing, drawing stretch processing, drawing stretch ironing processing, Seamless cans can be obtained.
  • the manufactured seamless can is appropriately subjected to a neck-in process or the like, and is subjected to a low temperature heat sterilization, a retort sterilization, or the like as appropriate depending on the type of the content through a content filling and lid winding process.
  • the seamless can of the present invention thus obtained, occurrence of metal exposure in the can body and corrosion (PET floating) in the tightening portion are effectively suppressed. Further, when a primer is provided between the inner surface resin coating and the metal plate, the adhesion between the metal plate and the inner surface resin coating is further improved, and the metal does not elute even when the acidic content is filled. Furthermore, the resin-coated metal plate used for forming this seamless can is mass-produced in that it uses a resin film that is excellent in productivity and handleability in its production. Very high value.
  • the sample data (the highest peak intensity value) was divided by the resin coating thickness to calculate the biaxial orientation value (cps / ⁇ m).
  • the X-ray diffraction intensity below the detection limit 70 cps or less) was set to 0 cps.
  • Metal exposure occurrence rate With respect to the obtained 200 cans of seamless cans, the metal exposure was measured by energizing using an enamelator, and the ratio (%) of cans having a current value of 0.5 mA or more was calculated.
  • the measurement condition of the enamellator was a voltage value of 6 V and a current value 4 seconds after the start of voltage application was taken as the measurement value.
  • As the electrolytic solution a solution obtained by adding 0.02% by weight of a surfactant to a 1% by weight sodium chloride aqueous solution was used.
  • the metal exposure occurrence rate was evaluated according to the following criteria. ⁇ (Low incidence): 1% or less ⁇ (Not high incidence): 1% above 3% or less ⁇ (High incidence): Over 3%
  • Example 1 [Production of resin-coated metal sheet]
  • TFS having a plate thickness of 0.185 mm (metal chromium amount 120 mg / m 2 , chromium in chromium hydrated oxide as 15 mg / m 2 ) was used.
  • PET / IA polyethylene terephthalate / isophthalate
  • An unstretched three-layer white film having a thickness of 16 ⁇ m was used as the outer resin coating film.
  • the surface layer of the outer surface resin coating film is made of PET / IA resin having an isophthalic acid copolymerization amount of 12 mol%, an intrinsic viscosity of 0.85 dL / g, and a melting point of 225 ° C., and its thickness is 2 ⁇ m and the titanium oxide concentration is 5% by weight. there were.
  • the intermediate layer was made of a PET / IA resin having an isophthalic acid copolymerization amount of 2 mol%, an intrinsic viscosity of 0.83 dL / g, and a melting point of 248 ° C., and its thickness was 12 ⁇ m and the titanium oxide concentration was 34% by weight.
  • the lower layer was made of a PET / IA resin having an isophthalic acid copolymerization amount of 15 mol%, an intrinsic viscosity of 0.9 dL / g, and a melting point of 215 ° C.
  • the thickness was 2 ⁇ m and the titanium oxide concentration was 0 wt%.
  • the inner resin coating film and the outer resin coating film are thermally bonded simultaneously to the inner and outer surfaces of the metal plate at a metal plate temperature of 260 ° C., and a wax-based lubricant is applied to the resin coated metal.
  • a plate was made.
  • the temperature of the laminating roll on the inner surface resin coating film side was 100 ° C.
  • the temperature of the laminating roll on the outer surface resin coating film side was 74 ° C.
  • the plate passing speed was 145 m / min.
  • the biaxial orientation degree of the inner surface resin coating in the obtained resin-coated metal plate was 3.0 cps / ⁇ m.
  • Example 2 A resin-coated metal plate was prepared in the same manner as in Example 1 except that the metal plate temperature during lamination was 255 ° C. and the biaxial orientation of the inner resin coating was 5.4 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 3 A resin-coated metal plate was prepared in the same manner as in Example 1 except that the temperature of the metal plate during lamination was 248 ° C. and the biaxial orientation degree of the inner resin coating was 8.0 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 4 The resin of the biaxially stretched film used as the inner surface resin coating film is homopolyethylene terephthalate, the metal plate temperature at the time of lamination is 290 ° C., and the biaxial orientation degree of the inner surface resin coating is 5.4 cps / ⁇ m.
  • a resin-coated metal plate was produced in the same manner as in Example 1. Seamless cans were produced and evaluated in the same manner as in Example 1.
  • Table 1 shows the film specifications for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 5 Polyethylene terephthalate / isophthalate (PET / IA) copolymer biaxially stretched film used as an inner resin coating film has an isophthalic acid copolymerization amount of 2 mol%, a metal plate temperature at the time of lamination of 280 ° C., and inner resin coating A resin-coated metal plate was prepared in the same manner as in Example 1 except that the biaxial orientation degree of was 5.4 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 6 Polyethylene terephthalate / isophthalate (PET / IA) copolymer biaxially stretched film used as an inner surface resin coating film has an isophthalic acid copolymerization amount of 15 mol%, a metal plate temperature at the time of lamination of 240 ° C., and inner surface resin coating A resin-coated metal plate was prepared in the same manner as in Example 1 except that the biaxial orientation degree of was 5.4 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 7 An epoxy-phenolic primer was previously applied to the inner resin coating film with a thickness of 0.8 ⁇ m, and the metal plate temperature during lamination was 255 ° C., and the biaxial orientation of the inner resin coating was 5.4 cps / ⁇ m.
  • a resin-coated metal plate was prepared in the same manner as in Example 1 except for the above. Seamless cans were produced and evaluated in the same manner as in Example 1.
  • Table 1 shows the film specifications for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 8 A resin-coated metal plate was prepared in the same manner as in Example 7 except that the primer preliminarily applied to the inner resin coating film was a polyester-phenol primer. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 9 As the metal plate, a JIS 3104 aluminum alloy plate having a plate thickness of 0.25 mm, which was subjected to a chromium phosphate surface treatment on both sides and having a chromium amount of 20 mg / m 2 , the metal plate temperature at the time of lamination was 260.
  • a resin-coated metal plate was prepared in the same manner as in Example 1 except that the temperature was set to 0 ° C. and the biaxial orientation degree of the inner surface resin coating was 5.4 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1.
  • Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Polyethylene terephthalate / isophthalate (PET / IA) copolymer biaxially stretched film used as an inner resin coating film has a two-layer structure consisting of a surface layer and a lower layer, and the surface layer has an isophthalic acid copolymerization amount of 2 mol%, inherent The viscosity is 0.83 dL / g, the thickness is 22 ⁇ m, the lower layer isophthalic acid copolymerization amount is 15 mol%, the intrinsic viscosity is 0.9 dL / g, the thickness is 6 ⁇ m, and the metal plate temperature during lamination is 280 ° C.
  • a resin-coated metal sheet was prepared in the same manner as in Example 1 except that the biaxial orientation degree of the inner surface resin coating was 4.3 cps / ⁇ m.
  • the biaxial orientation degree of the obtained inner surface resin coating was 4.3 cps / ⁇ m.
  • Seamless cans were produced and evaluated in the same manner as in Example 1.
  • Table 1 shows the film specifications for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • the polyethylene terephthalate / isophthalate (PET / IA) copolymer biaxially stretched film used as the inner surface resin coating film has an isophthalic acid copolymerization amount of 2 mol%, and the outer surface resin coating film consists of a surface layer and a lower layer.
  • An axially stretched bilayer white film was used.
  • the surface layer of the two-layer white film is an ethylene terephthalate / isophthalate (PET / IA) copolymer biaxially stretched resin having an isophthalic acid copolymerization amount of 12 mol%, an intrinsic viscosity of 0.70, and a melting point of 225 ° C., and its thickness is 2 ⁇ m, The titanium oxide concentration was 5% by weight.
  • the lower layer of the two-layer white film is an ethylene terephthalate / isophthalate (PET / IA) copolymer biaxially stretched resin having an isophthalic acid copolymerization amount of 12 mol%, and homopolyethylene terephthalate was blended to make the composition have a melting point of 240 ° C.
  • the thickness was 14 ⁇ m, the intrinsic viscosity was 0.66 dL / g, and the titanium oxide concentration was 30% by weight.
  • the temperature of the metal plate during lamination was 280 ° C., and a resin-coated metal plate was prepared in the same manner as in Example 1 except that.
  • the biaxial orientation degree of the obtained inner surface resin coating was 5.4 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1.
  • Table 1 shows the specifications of the film for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 1 A resin-coated metal plate was prepared in the same manner as in Example 1 except that the temperature of the metal plate during lamination was 265 ° C. and the biaxial orientation degree of the inner surface resin coating was less than 2.5 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the film specifications for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • Example 2 A resin-coated metal plate was prepared in the same manner as in Example 1 except that the temperature of the metal plate during lamination was 245 ° C. and the biaxial orientation degree of the inner resin coating was 8.9 cps / ⁇ m. Seamless cans were produced and evaluated in the same manner as in Example 1. Table 1 shows the film specifications for inner surface resin coating, the lamination conditions, and the degree of biaxial orientation of the inner surface resin coating. The evaluation results are shown in Table 2.
  • a Body hook radius b: Pressure ridge 1: Metal plate 2: Heating roll 3A: Laminating roll 3B: Laminating roll 4A: Inner surface resin coating film 4B: Outer surface resin coating film 5A: Supply roll 5B: Supply roll 11: Resin Coated metal plate 12: Water tank 13: Guide roller

Landscapes

  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Rigid Containers With Two Or More Constituent Elements (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

　La présente invention porte sur une feuille métallique revêtue de résine qui possède un revêtement de résine polyester formé sur au moins une surface d'une feuille métallique, la feuille métallique revêtue de résine étant caractérisée en ce que la résine polyester est une résine polyester à base de téréphtalate d'éthylène et en ce que le degré d'orientation biaxiale, qui est exprimé sous la forme d'une valeur obtenue en divisant le pic de résistance le plus élevé des pics d'une plage de 23 à 29° de l'angle de diffraction de rayons X 2θ d'une surface (100) du revêtement de résine polyester par l'épaisseur du revêtement de résine polyester, est dans la plage allant de 3,0 à 8,0 cps/µm. Cette feuille métallique revêtue de résine peut être facilement fabriquée en grandes quantités, et même lorsque les boîtes sont fabriquées par un processus de formation strict tel que l'emboutissage et l'étirage de paroi, l'incidence d'exposition de métal dans les surfaces internes des boîtes est faible, et la corrosion dans les parties de jonction être efficacement éliminée.
PCT/JP2014/079316 2013-11-06 2014-11-05 Feuille métallique revêtue de résine et boîte sans raccord WO2015068720A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-230230 2013-11-06
JP2013230230A JP6309741B2 (ja) 2013-11-06 2013-11-06 樹脂被覆金属板及びシームレス缶

Publications (1)

Publication Number Publication Date
WO2015068720A1 true WO2015068720A1 (fr) 2015-05-14

Family

ID=53041497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/079316 WO2015068720A1 (fr) 2013-11-06 2014-11-05 Feuille métallique revêtue de résine et boîte sans raccord

Country Status (2)

Country Link
JP (1) JP6309741B2 (fr)
WO (1) WO2015068720A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016093219A1 (fr) * 2014-12-12 2016-06-16 Ｊｆｅスチール株式会社 Feuille métallique revêtue de résine pour couvercle de boîte
US11241871B2 (en) 2016-05-10 2022-02-08 Novelis Inc. Laminated can end stock with elevated temperature annealing

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6650286B2 (ja) * 2016-02-08 2020-02-19 東洋鋼鈑株式会社 有機樹脂被覆鋼板およびその製造方法、並びにこの有機樹脂被覆鋼板を用いた缶及び缶蓋
EP3805122B1 (fr) * 2018-05-31 2023-07-05 Toyo Seikan Co., Ltd. Canette d'acier revêtue de résine et son procédé de fabrication
WO2021215498A1 (fr) * 2020-04-24 2021-10-28 東洋製罐グループホールディングス株式会社 Canette sans soudure
US20230202715A1 (en) * 2020-05-12 2023-06-29 Toyo Seikan Group Holdings, Ltd. Drawn/ironed can and coated metal sheet for drawn/ironed cans
JPWO2021235403A1 (fr) * 2020-05-22 2021-11-25
WO2022158593A1 (fr) * 2021-01-25 2022-07-28 東洋製罐グループホールディングス株式会社 Procédé de production de boîtes embouties et étirées, et boîtes embouties et étirées

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11138693A (ja) * 1997-11-14 1999-05-25 Toray Ind Inc 金属板ラミネート用ポリエステルフィルム
JPH11279294A (ja) * 1998-03-25 1999-10-12 Toyobo Co Ltd 樹脂被覆金属板用ポリエステルフィルム及びその使用方法
WO2000032680A1 (fr) * 1998-12-01 2000-06-08 Toyo Kohan Co., Ltd. Film de resine colore pour laminage d'une feuille metallique, et feuille metallique coloree comportant ledit film de resine colore
WO2001017768A1 (fr) * 1999-09-07 2001-03-15 Toyo Kohan Co., Ltd. Feuille metallique revetue de resine polyester et canette correspondante
JP2002255169A (ja) * 2001-02-28 2002-09-11 Toyo Seikan Kaisha Ltd 樹脂被覆シームレス缶
JP2003001760A (ja) * 2001-06-25 2003-01-08 Toyo Seikan Kaisha Ltd 樹脂被覆シームレス缶
JP2006282195A (ja) * 2005-03-31 2006-10-19 Toyo Seikan Kaisha Ltd 樹脂被覆金属缶及びその製造方法
WO2013099563A1 (fr) * 2011-12-26 2013-07-04 Ｊｆｅスチール株式会社 Tôle stratifiée et boîte de conserve pour aliments
WO2013157379A1 (fr) * 2012-04-19 2013-10-24 Ｊｆｅスチール株式会社 Feuille métallique stratifiée, et boîte de conserve pour nourriture
WO2014132541A1 (fr) * 2013-02-28 2014-09-04 Ｊｆｅスチール株式会社 Plaque métallique stratifiée pour canettes en deux parties et corps de stratifiée en deux parties
JP2014184619A (ja) * 2013-03-22 2014-10-02 Jfe Steel Corp ２ピース缶用ラミネート金属板および２ピースラミネート缶体

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11138693A (ja) * 1997-11-14 1999-05-25 Toray Ind Inc 金属板ラミネート用ポリエステルフィルム
JPH11279294A (ja) * 1998-03-25 1999-10-12 Toyobo Co Ltd 樹脂被覆金属板用ポリエステルフィルム及びその使用方法
WO2000032680A1 (fr) * 1998-12-01 2000-06-08 Toyo Kohan Co., Ltd. Film de resine colore pour laminage d'une feuille metallique, et feuille metallique coloree comportant ledit film de resine colore
WO2001017768A1 (fr) * 1999-09-07 2001-03-15 Toyo Kohan Co., Ltd. Feuille metallique revetue de resine polyester et canette correspondante
JP2002255169A (ja) * 2001-02-28 2002-09-11 Toyo Seikan Kaisha Ltd 樹脂被覆シームレス缶
JP2003001760A (ja) * 2001-06-25 2003-01-08 Toyo Seikan Kaisha Ltd 樹脂被覆シームレス缶
JP2006282195A (ja) * 2005-03-31 2006-10-19 Toyo Seikan Kaisha Ltd 樹脂被覆金属缶及びその製造方法
WO2013099563A1 (fr) * 2011-12-26 2013-07-04 Ｊｆｅスチール株式会社 Tôle stratifiée et boîte de conserve pour aliments
WO2013157379A1 (fr) * 2012-04-19 2013-10-24 Ｊｆｅスチール株式会社 Feuille métallique stratifiée, et boîte de conserve pour nourriture
WO2014132541A1 (fr) * 2013-02-28 2014-09-04 Ｊｆｅスチール株式会社 Plaque métallique stratifiée pour canettes en deux parties et corps de stratifiée en deux parties
JP2014184619A (ja) * 2013-03-22 2014-10-02 Jfe Steel Corp ２ピース缶用ラミネート金属板および２ピースラミネート缶体

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016093219A1 (fr) * 2014-12-12 2016-06-16 Ｊｆｅスチール株式会社 Feuille métallique revêtue de résine pour couvercle de boîte
JPWO2016093219A1 (ja) * 2014-12-12 2017-04-27 Ｊｆｅスチール株式会社 缶蓋用樹脂被覆金属板
US10399303B2 (en) 2014-12-12 2019-09-03 Jfe Steel Corporation Resin-coated metal sheet for can lids
US11241871B2 (en) 2016-05-10 2022-02-08 Novelis Inc. Laminated can end stock with elevated temperature annealing

Also Published As

Publication number Publication date
JP2015089643A (ja) 2015-05-11
JP6309741B2 (ja) 2018-04-11

Similar Documents

Publication Publication Date Title
JP6309741B2 (ja) 樹脂被覆金属板及びシームレス缶
EP2962951B1 (fr) Plaque métallique stratifiée pour canettes en deux parties et corps de stratifiée en deux parties
JPH0755552B2 (ja) 深絞り缶の製造方法
EP2799227B1 (fr) Feuille stratifiée et boîte de conserve pour aliments
JP2001246695A (ja) 樹脂被覆シームレス缶
EP2762304A1 (fr) Feuille métallique revêtue de résine pour contenant
AU2016240880B2 (en) Laminated metal sheet for container
KR102441780B1 (ko) 용기용 수지 피막 금속판
WO2018221385A1 (fr) Plaque métallique revêtue de résine pour récipient
JP2019014118A (ja) 樹脂被覆金属板、その樹脂被覆金属板を加工して成る金属缶
JP3262031B2 (ja) 積層体及びそれを用いた容器
JP5920279B2 (ja) ラミネート金属板、ラミネート金属板の製造方法および食品用缶詰容器
JP5609012B2 (ja) スチール製絞りしごき缶及びその製造方法
JP4366730B2 (ja) 製缶用積層体及びシームレス缶
US9758272B2 (en) Resin-coated seamless aluminum can
JP7195052B2 (ja) 容器用樹脂被覆金属板、その樹脂被覆金属板からなる容器、及びその樹脂被覆金属板の製造方法
JP4775532B2 (ja) 樹脂被覆シームレス缶
JP4079207B2 (ja) 樹脂被覆シームレス缶
JP4654617B2 (ja) リシール缶
JPH11216805A (ja) 積層体及びそれを用いた容器
JP2001253032A (ja) 熱可塑性樹脂フィルム、熱可塑性樹脂フィルム被覆金属板およびそれを用いた缶
JP2001341257A (ja) 金属板ラミネート用樹脂フィルムおよびラミネート金属板並びにその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14860228

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14860228

Country of ref document: EP

Kind code of ref document: A1