WO1998006568A1 - Plaque en metal revetue par une pellicule de resine multicouche pour impression de qualite - Google Patents

Plaque en metal revetue par une pellicule de resine multicouche pour impression de qualite Download PDF

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Publication number
WO1998006568A1
WO1998006568A1 PCT/JP1996/002299 JP9602299W WO9806568A1 WO 1998006568 A1 WO1998006568 A1 WO 1998006568A1 JP 9602299 W JP9602299 W JP 9602299W WO 9806568 A1 WO9806568 A1 WO 9806568A1
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WO
WIPO (PCT)
Prior art keywords
resin film
thermoplastic resin
film
white pigment
weight
Prior art date
Application number
PCT/JP1996/002299
Other languages
English (en)
Japanese (ja)
Inventor
Nobuyoshi Shimizu
Masanobu Matsubara
Atsuo Tanaka
Original Assignee
Toyo Kohan Co., Ltd.
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 Toyo Kohan Co., Ltd. filed Critical Toyo Kohan Co., Ltd.
Priority to JP10509572A priority Critical patent/JP3117729B2/ja
Priority to PCT/JP1996/002299 priority patent/WO1998006568A1/fr
Priority to AU66704/96A priority patent/AU6670496A/en
Publication of WO1998006568A1 publication Critical patent/WO1998006568A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives

Definitions

  • the present invention relates to a multilayer film-laminated metal sheet having excellent printing clarity and tool wear resistance. More specifically, an appropriate amount of pigment is added to a thermoplastic resin film used for packaging containers formed from a metal sheet laminated with a thermoplastic resin film to improve the light reflectance of the film and improve print clarity.
  • the present invention relates to a multi-layer film laminated metal plate having improved print clarity or appearance by laminating an enhanced resin film on the outer surface of a can or the surface of a metal plate corresponding to the outer surface of a lid. Background art
  • packaging materials have been required not only to store contents but also to have functions such as clarity of the color tone of a paint print for displaying the contents to be packaged.
  • a white printing base layer is usually provided to conceal the surface of the metal plate in order to improve the clarity and gloss of printing on the outer surface of the can.
  • this printing base layer is applied to a metal plate before it is formed into a can, and then printed.
  • a metal plate is formed into a can, then the printing base layer is painted, and then printing is performed.
  • the thickness of these white printing underlayers is in the range of about 5 to 15 / zm, depending on the type of metal plate. This film thickness is more than twice as large as that of the printed layer, and the reduction in film thickness contributes to reduction of can manufacturing energy and cost.
  • thermoplastic resin film when used instead of a paint, if the resin film used is a single-layer film, the film It is impossible to make the concentration of the white pigment more than a certain amount, and it is necessary to hide the surface of the metal plate by increasing the thickness of the film by making the addition amount of the white pigment in the film less than a certain amount. There is a problem. Furthermore, when a metal plate coated with a thermoplastic resin film is formed into a two-piece can by drawing or thinning drawing, the film contains a large amount of white pigment composed of hard particles such as titanium oxide. In addition, there is a problem that abrasion of dies and punches used for forming is increased.
  • the present invention suppresses the concealing effect of the metal plate surface while suppressing the amount of the white pigment added to a certain level or less.
  • the object is to increase and reduce the thickness of the film.
  • the problem to be solved by the present invention is to improve the appearance of the outer surface of the can by obtaining a multi-layered resin film-laminated metal plate for a can having excellent print clarity on the outer surface of the can.
  • Another problem to be solved by the present invention is to improve the appearance by using the multilayer film-laminated metal sheet of the present invention on the outer surface side of a can lid. Disclosure of the invention
  • the multilayer film-laminated metal sheet having excellent print clarity according to the present invention has a thickness of 1 to 30 m, which contains more than 0% by weight and not more than 20% by weight of a white pigment as an upper layer on at least one surface of the metal sheet. Poor compatibility between the thermoplastic resin film and the underlying thermoplastic resin 0.5 to 50% by weight of a thermoplastic resin film containing 0.5 to 50% by weight of an additive It is characterized by becoming.
  • the multilayer film-laminated metal plate of the present invention which has excellent print clarity, has a thickness of 1 to 3 containing at least one side of the metal plate and containing a white pigment serving as an upper layer in an amount of more than 0% by weight to 20% by weight or less.
  • 0-m thermoplastic resin film and a 5--30 / im thick thermoplastic resin film containing 0.5-50% by weight of an additive that forms a flat underlayer around it.
  • a multilayer film is a thickness of 1 to 3 containing at least one side of the metal plate and containing a white pigment serving as an upper layer in an amount of more than 0% by weight to 20% by weight or less.
  • 0-m thermoplastic resin film and a 5--30 / im thick thermoplastic resin film containing 0.5-50% by weight of an additive that forms a flat underlayer around it.
  • the multilayer film-laminated metal sheet of the present invention which has excellent print clarity, has a thickness of 1 to 30% which contains more than 0% by weight and 20% by weight or less of a white pigment to be an upper layer on at least one side of the metal sheet.
  • Thermoplastic resin film, and the thickness of the lower layer with fine voids dispersed therein It is coated with a multilayer film made of a thermoplastic resin film having a thickness of 5 to 30 m.
  • the multilayer film-laminated metal plate having excellent print clarity of the present invention has a thickness of from 1 to 30% containing at least one side of the metal plate containing more than 0% by weight and not more than 20% by weight of a white pigment as an upper layer.
  • the multilayer film-laminated metal plate having excellent print clarity of the present invention is a thermoplastic resin having a thickness of 1 to 30 m, containing 0 to 20% by weight of an upper white pigment on at least one surface of the metal plate.
  • the multilayer film-laminated metal plate having excellent print clarity of the present invention is a thermoplastic resin having a thickness of 1 to 30 m and containing, on at least one surface of the metal plate, 0 to 20% by weight of an upper white pigment.
  • the thermoplastic resin film of the intermediate layer is preferably a thermoplastic resin film having a thickness of 1 to 30 m containing 20 to 50% by weight of a white pigment.
  • the additive to be added to the thermoplastic resin of these multilayer film laminated metal sheets is one or two selected from mica, titanium oxide, calcium carbonate, barium sulfate, glass, polyolefin, and polytetrafluoroethylene. It is preferable that it is above.
  • thermoplastic resin film is formed into a multi-layer, and a layer for increasing the concealing effect is formed below the uppermost resin layer.
  • a layer for increasing the hiding effect a layer for forming voids is formed, or a layer in which the amount of the pigment added is greater than that of the uppermost layer.
  • a step of stretching a resin film may be used. No. That is, for example, when the multilayer film is a two-layer film, at least one side of the metal plate has poor compatibility between the thermoplastic resin film containing the white pigment to be the upper layer and the thermoplastic resin in the lower layer. When a multilayer film made of a thermoplastic resin film containing an additive is stretched, voids are formed around the lower additive. By laminating this multilayer film on a metal plate, a stretched film laminated metal plate having excellent print clarity on the outer surface of the can can be obtained.
  • additives having poor compatibility with the thermoplastic resin include mica, titanium oxide, calcium carbonate, barium sulfate, glass, polyolefin, and polytetrafluoroethylene.
  • thermoplastic resin laminated on the metal plate a polyester resin, a polyolefin resin, a polycarbonate resin, or a polyamide resin is preferable.
  • the polyester resin is more preferably a polyethylene terephthalate resin or a copolymerized polyester resin mainly composed of an ethylene terephthalate unit.
  • Titanium oxide white pigment must be added to the upper thermoplastic resin film, and mica, titanium oxide, calcium carbonate, barium sulfate, glass, polyolefin, and polytetrafluoroethylene are added to the lower thermoplastic resin film. Additives such as fluoroethylen must be added.
  • the multilayer film was provided with a thermoplastic resin film containing a larger amount of white pigment than the upper and lower layers as an intermediate layer between the upper thermoplastic resin film and the lower thermoplastic resin film. It may be a three-layer film.
  • the upper thermoplastic resin film contains a small amount of white pigment in order to further improve the sharpness of printing and reduce the amount of wear of the forming tool.
  • the amount of the additive or the white pigment contained in the lower thermoplastic resin film is small.
  • the intermediate layer is provided in this manner, it is not necessary to further increase the thickness of the upper and lower thermoplastic resin films, and it is more preferable that each of the thermoplastic resin films is as thin as possible within a preferable range. .
  • the intermediate layer may be further exposed to a layer having a different content of the above-mentioned white pigment and / or an additive having poor compatibility with the thermoplastic resin within a range that does not impair the cost. It may be a multi-layer film with three or more layers.
  • the multilayer film-laminated metal plate of the present invention having excellent print clarity can be obtained.
  • a white film is used as a printing base layer on the outer surface of the can.
  • the purpose of using such a white film as a printing base is to conceal the color tone of a metal plate having been subjected to a surface treatment, and the more excellent the white, the better the printing clarity.
  • the degree of whiteness of the surface of a metal plate on which a thermoplastic resin film having a white pigment is laminated is correlated with the diffuse reflection value (L * indicates Elster, representing lightness), and the diffuse reflection L 'value The larger the value, the whiter the surface of the thermoplastic resin film-laminated metal plate.
  • the term “direct” here refers to the diffusion when incident light is incident at an angle of 10 degrees with respect to the normal direction of the sample using, for example, a spectral colorimeter SZ-110 manufactured by Nippon Denshoku Co., Ltd. This is a value obtained by measuring a reflection component.
  • thermoplastic resin film-coated metal plate having a white pigment improves the concealment of the underlying metal, and as a result, improves the print clarity.
  • it is effective to increase the white pigment concentration, but there is a limit due to reasons for film formation.
  • the amount of the white pigment contained in the thermoplastic resin film is increased, the amount of abrasion of the forming tool is increased when the resin film-coated metal plate is subjected to processing such as drawing, which is not preferable.
  • the multilayer film of the present invention When the multilayer film of the present invention is a two-layer film, it has a titanium oxide-based white pigment in an amount of more than 0% by weight and not more than 20% by weight as an upper layer (a layer to be the outermost layer). Containing 0.5 to 50% by weight of a layer of a thermoplastic resin film having a thickness of up to 30 m, and an additive which generates voids by stretching as a lower layer (referred to as a layer in contact with the metal plate); or Thickness containing more than 20% by weight and not more than 50% by weight of a white pigment. It is preferably a multilayer film composed of m thermoplastic resin film layers.
  • the multilayer film comprises a thermoplastic resin film having a thickness of 1 to 30 m containing 0 to 20% by weight of a white pigment as an upper layer, and a lower layer in the above-mentioned two-layer film.
  • the lower layer is a thermoplastic resin film with a thickness of 1 to 30 jam containing 0 to 20% by weight of the same white pigment as the upper layer and between the upper and lower layers.
  • a three-layer film in which a thermoplastic resin film containing the above white pigment is provided as an intermediate layer may be used. When this intermediate layer is provided, the white pigment contained in the upper thermoplastic resin film is reduced in order to further improve the clarity of printing and reduce the abrasion of the forming tool.
  • the thickness of the upper and lower thermoplastic resin films does not need to be particularly large, and it is more preferable that each of the films has a thickness within a suitable range and is as thin as possible.
  • thermoplastic resin film of the intermediate layer is preferably a single-layer resin film having a thickness of 1 to 30 m to which 20 to 50% by weight of a titanium oxide-based white pigment is added.
  • additives that form voids have poor compatibility with the thermoplastic resin, and examples thereof include mica, titanium oxide, calcium carbonate, barium sulfate, glass, polyolefin, and polytetrafluoroethylene.
  • thermoplastic resins The compatibility of additives with thermoplastic resins is qualitative, but in the case of organic compounds, it is possible to select the solubility parameter as an indicator. In the case of an inorganic compound, it is possible to select a contact angle or the like as an index.
  • the purpose of adding these additives is to form thin voids at the interface between the resin and the additive when the thermoplastic resin film is stretched and formed. These voids have a great effect on light scattering in the resin film.
  • Light rays entering the thermoplastic resin film are reflected by a white pigment and are recognized as a white color.
  • Light that has not collided with the white pigment is reflected by the underlying metal surface and emits a metal-specific color tone.
  • the light reflectivity of pigments and metal surfaces depends on the refractive index of the thermoplastic resin film, And the refractive index difference of the metal surface.
  • the refractive index of a thermoplastic resin film is in the range of 1.5 to 1.6, and that of titanium oxide is in the range of 2.4 to 3.
  • the refractive index of the metal surface varies depending on the type of metal and the type of surface treatment. Therefore, titanium oxide having a large difference in refractive index is selected as a white pigment.
  • a difference in refractive index is important.
  • the reflectance becomes 1 when the incident angle exceeds a certain value according to the difference in the refractive index, so that the refractive index becomes 1.5 to 1.5. If a void having the minimum refractive index (1.0) exists in the thermoplastic resin film of No. 6, many light rays are reflected at the interface between the film and air. Therefore, the amount of light reaching the underlying metal surface is reduced, and the concealment property is enhanced.
  • the purpose of forming a layer having a white pigment of more than 0% by weight and not more than 20% by weight in the upper layer is to scatter incident light with the white pigment in this layer and to scatter reflected light from the lower layer.
  • Inorganic and organic pigments can be used as the white pigment, depending on the application.However, it is clear that a titanium oxide pigment with a particle size of 0.2 to 0.3 m is used. It is more preferable in terms of providing properties.
  • white pigment is not added, even if an additive such as mica is used in the lower resin film, the desired clarity of printing cannot be secured because the concealing property of the base is insufficient.
  • the film strength decreases, so the addition range is limited to more than 0% by weight and not more than 20% by weight. More preferably, it is 5 to 20% by weight.
  • the film thickness of the upper layer is required to be at least 1 m or more to ensure the concealment of the underlayer, and it is expensive if it is 30 ⁇ m or more. More preferably, it is 5 to 15 zm.
  • thermoplastic resin film serving as the upper layer As described above, by adding a white pigment to the thermoplastic resin film serving as the upper layer, the underlying metal surface is concealed. improves. However, as described above, excessive addition of the white pigment makes it difficult to form a resin film and increases the wear of the tool during molding. In order to overcome this drawback, a thermoplastic resin film containing an amount of white pigment that satisfies a certain hiding effect and abrasion resistance of the tool is used as the upper layer, and underneath, a larger amount of white pigment is added than the upper layer. By forming a multilayer resin film with a plastic resin film as an intermediate layer, it is possible to form a resin film, improve the concealment effect of the base, and satisfy the wear resistance of the tool. Was.
  • the amount of the white pigment contained in the entire multilayer resin film it is possible to increase the amount of the white pigment contained in the entire multilayer resin film, and to increase the amount of the white pigment contained in the resin film of the intermediate layer to increase the amount of the white pigment.
  • the amount of the white pigment contained in the resin film can be reduced, and in some cases, can be omitted. Further, by improving the effect of hiding the base by the intermediate layer, it is possible to reduce the amount of additives or white pigments contained in the resin film of the lower layer, and in some cases, to add no additives, Also improves the adhesion to the metal plate.
  • the intermediate layer may be a single-layer film, or a white pigment content to further improve the film forming property of the resin film, the effect of concealing the surface of the underlying metal, and the adhesion to the metal plate.
  • a multilayer film composed of at least two layers, each of which has a different content of the additive having poor compatibility with the above-mentioned thermoplastic resin.
  • the intermediate layer is a single-layer resin film, it is contained in the resin film, depending on the content of the white pigment in the upper resin film and the additive or white pigment in the lower resin film.
  • the amount of the white pigment to be used is preferably in the range of 20 to 50% by weight.
  • the content is less than 20% by weight, the effect of hiding the surface of the underlying metal is insufficient, and if it exceeds 50% by weight, the film formability of the resin film is significantly reduced.
  • a more preferred range is 25 to 40% by weight.
  • the thickness of the resin film must be at least 1 jm or more in order to ensure the concealment of the base, and if it exceeds 30 tm, film formation becomes difficult and film formation cost increases. More preferably, it is in the range of 5 to 15 zm.
  • the amount of the white pigment contained in the resin film as the upper layer is more than 0% by weight and less than 50% by weight, and the amount of the white pigment in the lower layer is less than 50% by weight.
  • the amount of the white pigment contained in the film is preferably more than 0% by weight and less than 50% by weight.
  • White on the upper and lower resin films If no pigment is added, the effect of hiding the surface of the underlying metal is insufficient, and if it exceeds 50% by weight, the film-forming properties of the resin film are significantly reduced. A more preferred range is 25 to 40% by weight.
  • the thickness of each resin film is required to be at least 1 / zm or more in order to secure the concealing property of the base. If it exceeds 20, the concealing effect is saturated and the film forming cost increases. More preferably, it is in the range of 2 to 10 / m.
  • the lower layer is a thermoplastic resin film layer having a thickness of 1 to 30 and containing 0.5 to 50% by weight of an additive having poor compatibility with the thermoplastic resin film. This is for forming fine voids.
  • the inorganic additives having poor compatibility with the thermoplastic resin include mica, titanium oxide, calcium carbonate, barium sulfate, and glass.
  • the organic additive include polyolefin and polytetrafluoroethylene.
  • mica such as mica which is oriented in a plane to form a void.
  • the shape of the additive may be spherical or scaly, but the effect is particularly large when the additive is scaly.
  • the additive When the additive is scaly mica, a size of 0.5 to 50 m, preferably 1 to 10 m can be used. If the additive is granular, a particle size of 0.1 to 3 // m is appropriate. These additives have an effect almost proportional to the amount added. When the amount is less than 0.5% by weight, the effect of reflection is low, and when the amount is more than 50% by weight, the film strength is reduced. Therefore, the addition range is limited to 0.5 to 50% by weight. A more preferred range is 5 to 20% by weight. In order to conceal the color of the underlying metal, the thickness of the lower film must be 1 // m or more, and if it is 30 m or more, the cost is high, so it is specified as 1 to 30 m. A more preferred range is from 1 to 10 / m.
  • the lower layer may be a thermoplastic resin film having a thickness of 1 to 30 im containing 0 to 20% by weight of a white pigment similarly to the upper layer.
  • the white pigment is preferably small in order to improve the adhesion between the base metal and the thermoplastic resin film, and may not be added.
  • the film strength is reduced and the adhesion between the base metal and the thermoplastic resin film is also deteriorated, so the addition range is limited to 0 to 20% by weight. More preferably, it is 0 to 10% by weight.
  • the film thickness must be more than 1 / m, and higher than 30; ⁇ m It is specified as 1 to 30 m because of the cost. A more preferred range is 1 to 10 °.
  • both sides of the metal plate may be coated with the multilayer resin film layer of the present invention, or only the outer side of the can is coated with the multilayer resin film layer, and the inner surface of the can May be coated with an arbitrary resin.
  • metal plate a steel plate or an aluminum alloy plate subjected to various surface treatments can be used.
  • thermoplastic resin examples include polyester resin, polyolefin resin, polycarbonate resin, and polyamide resin.
  • Various polyester resins can be used.Specifically, a copolymerized polyester resin mainly composed of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthate, and ethylene terephthalate units, or A polyester resin composed of these mixtures is exemplified.
  • thermoplastic resin is a polyolefin resin, polypropylene, polyethylene, a resin obtained by blending them, and the like are applicable to the present invention.
  • thermoplastic resin is a polycarbonate resin, it is preferably an aromatic polycarbonate resin from the viewpoint of heat resistance, and particularly preferably a bisphenol-A-polycarbonate resin.
  • polyamide resin 6-nylon, 6,6-nylon, 6-6,6-copolymer nylon, 6,10-nylon, 7-nylon, 11-nylon and the like are applicable to the present invention.
  • thermoplastic resin film As a method of coating the above-mentioned thermoplastic resin film on a metal plate, a method of directly laminating a film stretched and oriented by a conventional method on both surfaces of the metal plate by heat fusion, or a method of laminating via an adhesive, and There are methods using these methods in combination, and any of these methods can be applied as the method for producing the resin film-coated metal sheet of the present invention.
  • thermoplastic resin film on a metal plate via an adhesive layer is more preferable from the viewpoint of improving the processing adhesion.
  • Known adhesives can be used, but a thermosetting polymer composition having an epoxy group in the molecule is more preferable. Alternatively, it may be applied and dried on the surface of the thermoplastic resin film in contact with the metal plate, or may be applied and dried on the surface of the metal plate.
  • any resin can be applied on the inner side of the can, but when paint is used instead of thermoplastic resin, an appropriate amount of phenol resin or amide is used as a curing agent in epoxy resin. It is preferable to use a thermosetting polymer composition having an epoxy group in the molecule, in which a resin, an acrylic resin, or the like is mixed.
  • a biaxially stretched copolyester resin film consisting of 88 mol% of polyethylene terephthalate and 12 mol% of polyethylene isophthalate is coated on the inner side of the can on a thin tin-plated steel sheet (thickness: 25 / zm) as the upper layer on the outer surface of the can, a polyester resin film having the same composition as described above having the white pigment shown in Table 1, and the same as the above having the mica powder shown in Table 1 as the lower layer
  • a two-layer stretched film composed of a polyester resin film having the composition was laminated. After lamination, multi-color printing of 2 m thick red, blue, green, yellow, and gold reference colors was performed.
  • the striped film-laminated steel sheet was cut into a blank size for a welding can to obtain a three-piece welding can.
  • the whiteness of the base before printing was evaluated based on the value obtained by measuring the diffuse reflection L * with a spectral color difference meter SZS- ⁇ 90 manufactured by Nippon Denshoku Co., Ltd. Since this diffuse reflection value varies depending on the measurement model and measurement conditions, it should not be judged based on the absolute value. However, for convenience, 84 or more were accepted for both the can body and can lid.
  • the print clarity of the outer surface of the can after making cans was evaluated by visually inspecting cans with multi-color printing of red, blue, green, yellow, and gold reference colors. From the clearest case to giving a dark and dull feeling, the evaluation was made in four steps as follows.
  • a single-layer stretched film of 20 m thick bisphenol A poly-polycarbonate resin is applied to the inner surface of the can, and an upper layer is applied to the outer surface of the can.
  • Each of the two-layer stretched films made of the polycarbonate resin film having the same composition as described above was laminated. After lamination, about 5 Omg Zm 2 of paraffin wax was applied on both sides, and the following processing was performed.
  • a blank having a diameter of 179 mm was punched, and then a drawn can having a diameter of 10 O mm was obtained.
  • a redrawing can with a diameter of 8 O mm was made by redrawing.
  • This redrawn can was further made into a thinned deep drawn can having a can diameter of 66 mm.
  • multicolor printing of red, blue, green, yellow, and gold reference colors of 2 m in thickness was performed, and the print sharpness of the outer surface of the can was evaluated in the same manner as in Example 1.
  • An ordinary thin tin-plated steel sheet has a 10-m-thick epoxy / phenol paint on the inner side 2 of the can and a white pigment shown in Table 3 as an upper layer on the outer side of the can. Then, a two-layer stretched film composed of a resin film obtained by blending a polytetrafluoroethylene resin shown in Table 3 as a lower layer with a polyester resin of the same type as described above as a lower layer was laminated. Thin tin-plated steel sheets having these resin films laminated were canned under the same conditions as in Example 1, and the print clarity on the outer surface of the can after the can was evaluated in the same manner as in Example 1.
  • Example 1 The same biaxially stretched copolyester resin film as shown in Example 1 was coated on the inner surface of the aluminum alloy plate with the white pigment shown in Table 4 as the upper layer on the outer surface.
  • An aluminum alloy plate on which these resin films were laminated was canned under the same conditions as in Example 2, and the print clarity on the outer surface of the can after the can was evaluated in the same manner as in Example 1.
  • a 20-zm-thick single-layer stretched film of bisphenol A polycarbonate resin is applied to the inner surface of the can lid of the aluminum alloy plate, and the white pigment shown in Table 5 is applied as an upper layer to the outer surface.
  • Bisphenol A polycarbonate resin film and a two-layer stretched film of the same type of polycarbonate resin film having calcium carbonate shown in Table 5 as a lower layer are laminated, and the whiteness of the outer surface of the can lid (Underground concealment property) was evaluated in the same manner as in Example 1.
  • a single-layer stretched film made of the same bisphenol A polycarbonate resin as shown in Example 5 was applied to the inner surface of the can lid of the electrolytic chromic acid-treated steel sheet, and an upper layer was applied to the outer surface as shown in Table 6.
  • Example 2 The same biaxially stretched copolyester resin film as shown in Example 1 was applied to the inner surface of the can of electrolytic chromic acid-treated steel sheet, and the white pigment shown in Table 7 was applied to the outer surface of the can as the upper layer. And a two-layer stretched film composed of a copolymerized polyester resin film having the same composition as the above and having a white pigment shown in Table 7 as a lower layer. After lamination, a thinned deep drawn can was made under the same conditions as shown in Example 2. After making the can, multicolor printing of 2 x m thick red, blue, green, yellow, and gold reference colors was performed, and the print clarity of the outer surface of the can was evaluated in the same manner as in Example 1.
  • Example 2 The same biaxially stretched copolyester resin film as shown in Example 1 was applied to the inner surface of the electrolytic chromic acid-treated steel sheet on the inner surface side of the can, and the upper surface layer of the white pigment shown in Table 8 was applied to the outer surface of the can.
  • a polyester resin film of the same composition as shown in Table 8 as the intermediate layer, and the same as above with the mica powder shown in Table 8 as the lower layer A three-layer stretched film composed of a copolymerized polyester resin film having the composition was laminated. After the lamination, a can was made into a thin-walled deep-drawn can under the same conditions as shown in Example 2. Multicolor printing of red, blue, green, yellow, and gold reference colors having a thickness of 2 jum after can making was performed, and the print clarity of the outer surface of the can was evaluated in the same manner as in Example 1.
  • Example 9 The same biaxially stretched copolyester resin film as shown in Example 1 was applied to the inner surface of the electrolytic chromic acid-treated steel sheet on the inner surface side of the can, and the upper surface layer of the white pigment shown in Table 9 was applied to the outer surface of the can. Contains or does not contain a copolymerized polyester resin film having the same composition as the above, a polyester resin film having the same composition as shown in Table 9 as an intermediate layer, and a white pigment shown in Table 9 as a lower layer, or Not Included Three-layer stretched films made of a copolymerized polyester resin film having the same composition as described above were laminated.
  • Example 2 After lamination, a can was made into a thin-walled deep-drawn can under the same conditions as shown in Example 2. After making the can, multicolor printing of 2 im red, blue, green, yellow, and gold reference colors was performed, and the print clarity of the outer surface of the can was evaluated in the same manner as in Example 1.
  • the same biaxially stretched copolyester resin film as shown in Example 1 was applied to the surface of the electrolytic chromic acid-treated steel sheet on the inner surface of the can, and the upper surface of the can outer surface of the can was the white color shown in Table 10
  • a polyester resin film having the same composition as the above having the white pigment shown in Table 10 as the lower layer, and a copolymerized polyester resin having the same composition as the above containing or not containing the glass powder shown in Table 10 as the lower layer Four-layer stretched films made of films were laminated.
  • Example 2 After lamination, a thinned deep drawn can was made under the same conditions as shown in Example 2. After making the can, multicolor printing of red, blue, green, yellow, and gold reference colors having a thickness of 2 _t m was performed, and the print clarity of the outer surface of the can was evaluated in the same manner as in Example 1.
  • Example 11 The same composition as that of the ordinary thin tin-plated steel sheet containing the same film as in Example 1 on the inner side of the can and the upper layer on the outer side of the can containing the white pigment shown in Table 11 And a two-layer stretched film of a 5 jm-thick copolyester resin film having a thickness of 5 jm and containing 0.3% by weight of mica powder as a lower layer.
  • the can was made under the same conditions as in Example 1, and the print clarity on the outer surface of the can was evaluated in the same manner as in Example 1.
  • Example 2 On a normal electrolytic chromic acid-treated steel sheet, a 20-zm bisphenol A polycarbonate resin film of the same thickness as in Example 2 was applied to the inner surface of the can, as shown in Table 11 as the upper layer on the outer surface of the can.
  • the resulting two-layer stretched film was laminated.
  • a can was made under the same conditions as in Example 2, and after printing in the same manner as in Example 2, the print clarity on the outer surface of the can was evaluated in the same manner.
  • a normal thin tin-plated steel sheet has a 10-m-thick epoxy phenolic paint on the inner surface of the can and a white pigment shown in Table 11 as an upper layer on the steel plate on the outer surface of the can
  • Two-layer stretched films were laminated.
  • the resin film-laminated thin tin-coated steel sheet was canned under the same conditions as in Example 1, and the print clarity on the outer surface of the can after the can was similarly evaluated.
  • Example 1 The same biaxially stretched copolymerized polyester resin film as shown in Example 1 was used on the inner surface of the aluminum alloy plate and the white pigment shown in Table 11 was used as the upper layer on the outer surface of the can.
  • Two layers comprising a copolymerized polyester resin film of the same composition as shown in Example 1 and a 3 m-thick polyester resin film having a thickness of 0.3% by weight of barium sulfate as a lower layer.
  • the stretched films were laminated.
  • An aluminum alloy plate on which these resin films were laminated was canned under the same conditions as in Example 2, and the print clarity on the outer surface of the can after the can was evaluated in the same manner as in Example 1.
  • a single-layer stretched film of bisphenol A polycarbonate resin with a thickness of 20 / zm is shown on the inner surface of the aluminum alloy plate can lid as shown in Table 11 as an upper layer on the outer surface.
  • a two-layer drawing comprising a bisphenol A polycarbonate resin film having a white pigment and a bisphenol A polycarbonate resin film of the same type as above having a thickness of 3 zm having 0.3% by weight of calcium carbonate as a lower layer. The films were laminated, and the whiteness of the outer surface of the can lid (underlaying property) was evaluated in the same manner as in Example 1.
  • Example 7 On the inner surface of the can lid of the electrolytic chromic acid-treated steel sheet, a single-layer stretched film made of the same bisphenol A polypolycarbonate resin as shown in Example 5 was applied to the outer surface.
  • Bisphenol A of the same type as above containing 10 / m thick bisphenol A polyphenol resin film having a white pigment shown in Table 11 as the upper layer and 0.3% by weight of polyolefin (polypropylene) as the lower layer.
  • a two-layer stretched film consisting of a 3 / m-thick film blended with a polycarbonate resin film was laminated, and the whiteness on the outer surface of the can lid (underground opacity) was evaluated in the same manner as in Example 1. . (Comparative Example 7)
  • Example 11 The same biaxially stretched copolyester resin film as shown in Example 1 was applied to the inner surface of the electrolytic chromic acid-treated steel sheet on the inner surface of the can, and the upper surface of the outer surface of the can was white as shown in Table 11
  • a can was made into a thinned deep drawn can under the same conditions as described in Example 2. Multicolor printing of red, blue, green, yellow, and gold reference colors with a thickness of 2 m after the can was made, and the print clarity of the outer surface of the can was evaluated in the same manner as in Example 1.
  • Example 2 On the electrolytic chromic acid-treated steel sheet, a bisphenol A polycarbonate resin film of the same thickness of 20 am as in Example 2 is shown on the inner side of the can, and Table 11 is shown on the outer side of the can.
  • a 1 m-thick single-layer stretched film of a polycarbonate resin film of the same type as above having a white pigment was laminated. After lamination, the can was made under the same conditions as in Example 2.After the can was made, multicolor printing of the red, blue, green, yellow, and gold reference colors was performed, and the printing on the outer surface of the can was the same as in Example 1. Was evaluated.
  • Example 2 On the electrolytic chromic acid-treated steel sheet, the same biaxially stretched copolymerized polyester resin film as shown in Example 1 was applied to the inner surface of the can, and the upper layer was applied to the outer surface of the can. Then, a copolymerized polyester resin film having the same composition as described above without containing the white pigment shown in Table 12; a polyester resin film having the same composition as described above having the white pigment as the intermediate layer; and having the mica powder as the lower layer A three-layer stretched film composed of a copolymerized polyester resin film having the same composition was laminated.
  • Example 2 After lamination in this manner, the can was made under the same conditions as in Example 2.After making the can, multicolor printing of 2 m thick red, blue, green, yellow, and gold reference colors was performed to improve the print clarity on the outer surface of the can. Evaluation was performed in the same manner as in Example 1.
  • PTFE * Polytetrafluoroethylene resin Table 4 Characteristics of the outer resin film Upper layer Lower layer White filler Printing material Luminous number of the film White pigment Thickness Halium sulfate Thickness Diffusivity (weight) %) (M) (wt%) (/ m)
  • the multilayer film-laminated metal plate of the present invention even if the thickness of the resin film layer having a white pigment is reduced, the two-piece can and the three-piece can or the base having excellent print clarity on the outer surface of the can can be obtained. It becomes possible to produce a can lid having excellent concealing properties.

Landscapes

  • Laminated Bodies (AREA)

Abstract

Plaque en métal revêtue par une pellicule de résine multicouche, dans le but d'effectuer une impression de qualité, ce qui économise l'usure des outils qu'on utilise afin de façonner cette plaque en un récipient métallique. Au moins un côté de la plaque en métal est revêtu par une pellicule multicouche comprenant une couche supérieure de résine thermoplastique contenant un pigment blanc et une couche inférieure de résine thermoplastique contenant des additifs possédant une compatibilité inférieure avec la résine thermoplastique afin d'améliorer la qualité de réflexion de la pellicule, ce qui augmente la qualité de l'impression.
PCT/JP1996/002299 1996-08-14 1996-08-14 Plaque en metal revetue par une pellicule de resine multicouche pour impression de qualite WO1998006568A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP10509572A JP3117729B2 (ja) 1996-08-14 1996-08-14 印刷鮮明性に優れる複層フィルム積層金属板
PCT/JP1996/002299 WO1998006568A1 (fr) 1996-08-14 1996-08-14 Plaque en metal revetue par une pellicule de resine multicouche pour impression de qualite
AU66704/96A AU6670496A (en) 1996-08-14 1996-08-14 Metal sheet coated with multilayer resin film for quality printing

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1996/002299 WO1998006568A1 (fr) 1996-08-14 1996-08-14 Plaque en metal revetue par une pellicule de resine multicouche pour impression de qualite

Publications (1)

Publication Number Publication Date
WO1998006568A1 true WO1998006568A1 (fr) 1998-02-19

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PCT/JP1996/002299 WO1998006568A1 (fr) 1996-08-14 1996-08-14 Plaque en metal revetue par une pellicule de resine multicouche pour impression de qualite

Country Status (3)

Country Link
JP (1) JP3117729B2 (fr)
AU (1) AU6670496A (fr)
WO (1) WO1998006568A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH079615A (ja) * 1993-06-28 1995-01-13 Toyo Kohan Co Ltd 複合樹脂被覆金属板およびその製造法
JPH0752351A (ja) * 1993-08-17 1995-02-28 Diafoil Co Ltd 金属ラミネート用積層白色ポリエステルフイルム
JPH0825550A (ja) * 1994-07-14 1996-01-30 Toyo Kohan Co Ltd 容器用二層樹脂被覆鋼板

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH079615A (ja) * 1993-06-28 1995-01-13 Toyo Kohan Co Ltd 複合樹脂被覆金属板およびその製造法
JPH0752351A (ja) * 1993-08-17 1995-02-28 Diafoil Co Ltd 金属ラミネート用積層白色ポリエステルフイルム
JPH0825550A (ja) * 1994-07-14 1996-01-30 Toyo Kohan Co Ltd 容器用二層樹脂被覆鋼板

Also Published As

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JP3117729B2 (ja) 2000-12-18
AU6670496A (en) 1998-03-06

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