JPH0578411B2 - - Google Patents

Description

[Detailed description of the invention]

(a) Field of Industrial Application The present invention relates to a method for producing a metallized laminated film by extrusion laminating an olefin resin onto a metallized resin film, and particularly provides a metallized laminated film useful as various packaging materials. It is something to do. (b) Conventional technology Conventionally, metals obtained by extrusion laminating an olefin resin such as polyethylene on the metal surface of a metal-deposited film in which a metal such as aluminum is deposited on a resin film base material such as polypropylene or polyethylene terephthalate have been produced. Vapor-deposited laminated films are widely used as various packaging materials due to their excellent gas-barrier properties, light-shielding properties, and aesthetic appeal. However, since olefin-based resins inherently have the drawback of poor adhesion, such metal-deposited laminated films are manufactured by applying pre-treatment such as anchor coating to the surface of the metal-deposited film at temperatures of 300 to 330°C.
It is manufactured by extrusion laminating olefin resin at a moderately high temperature, but during this lamination process, countless fine cracks often occur in the deposited film, which significantly deteriorates the appearance of the laminated film. This not only causes problems, but also causes the problem that the intended gas barrier properties cannot be obtained. Furthermore, depending on the material of the film to be deposited, there is a problem that the adhesive strength between the film to be deposited and the deposited film is reduced by lamination. As a gas barrier film, the wall thickness is 6~
It is also known that olefin resin is laminated by melt extrusion on a laminated film based on BOPP, PET, etc. with 15μ aluminum foil adhered to it.
This laminate is made into a bag, filled with the contents, heat-sealed, and then transported in a cardboard box.As a result of repeated bending of the film due to impact during transport, pinholes appear in the aluminum foil. This has the disadvantage that the gas barrier properties of the bag deteriorate (see Comparative Application Example 1). Furthermore, aluminum foil has a thick wall thickness of 6 to 15 μm, resulting in high cost. (c) Problems to be Solved by the Invention The present invention has been made in view of the above-mentioned drawbacks in producing a metallized laminated film by extrusion laminating an olefin resin on a metallized film, and it solves the following problems: To provide a method for manufacturing a metal vapor-deposited laminated film which not only has excellent adhesive strength with a laminate layer but also eliminates the occurrence of cracks in the metal vapor-deposited film and eliminates a decrease in adhesive strength between the film to be vapor-deposited and the vapor-deposited film. The purpose is to (d) Means for solving the problems The method for producing a metal-deposited laminated film of the present invention includes:
In manufacturing a metal-deposited laminated film by extrusion laminating an olefin-based resin onto a metal-deposited resin film with a thickness of 100 to 1000 angstroms, the olefin-based resin is extruded from an extruder die at a resin temperature of 150 to 290°C and melted. The method is characterized in that the molten thin film is formed into a thin film, and then the molten thin film is treated with ozone, and then pressure-bonded and laminated onto the metal surface of the resin film on which the metal is vapor-deposited without using an anchor cord agent. In the present invention, the metal-deposited resin film refers to polyethylene, polypropylene, polyethylene terephthalate, polyamide, polystyrene,
After performing corona discharge treatment on one or both sides of a stretched or unstretched film or sheet of thermoplastic resin such as polycarbonate or polyvinyl chloride, metal such as aluminum, copper, gold, or molybdenum is applied. , the thickness of the deposited film is 100 to 1000 angstroms (Å) by a known deposition method such as vacuum deposition, sputtering, or ion beam method.
Preferably, it refers to a material deposited to a thickness of about 200 to 600 Å. In addition, as the olefin resin to be extrusion laminated, low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer having a melt flow rate of about 1 to 300 g/10 minutes, preferably about 3 to 100 g/10 minutes, Ethylene-(meth)acrylic acid ester copolymer, ethylene-(meth)acrylic acid copolymer and ionic copolymer whose acid moiety is neutralized with metal ions, ethylene-
Examples include ethylene resins such as propylene copolymers and ethylene-butene-1 copolymers; propylene resins such as polypropylene, propylene-ethylene copolymers, and propylene-butene-1 copolymers. Among these, ethylene resin is preferred. In the present invention, when extruding the olefin resin from an extruder die to form a molten thin film, it is essential that the resin temperature immediately below the die is 150 to 290°C, preferably 180 to 280°C, and preferably 220 to 290°C. 260
It is particularly preferable to set the temperature to ℃. If the resin temperature is less than 150°C, the spreadability of the resin will be poor, and not only will a molten thin film not be obtained smoothly, but the adhesive strength with the metal-deposited film will be insufficient. Furthermore, if the temperature exceeds 290°C, cracks will occur in the vapor deposited film as a metal vapor deposited laminated film, or the adhesive strength between the film to be vapor deposited and the vapor deposited film will significantly decrease. Further, in the present invention, when the molten thin film is pressure-bonded and laminated onto the metal surface of the metallized film, it is essential to subject the molten thin film to ozone treatment. Ozone treatment is performed by directing ozone-containing gas (air, etc.) from a nozzle or slit-shaped outlet toward the surface of the molten thin film, toward the surface of the metallized film, or by pressing the molten thin film and the metallized film together. It is done by spraying towards the area. At this time, the ozone concentration in the sprayed gas is 1 g/m ³
The above is preferable, more preferably 3 g/m ³ or more, and 10 g/m ³ or more is preferable in terms of being able to respond to various laminating conditions. The spraying amount is preferably 0.03/min/cm or more, more preferably 0.1/min/cm relative to the width of the molten thin film.
That's all. In this case, it is necessary to avoid increasing the flow rate to an extremely high level because this will cause the molten thin film to oscillate and become uneven in thickness. The method for producing a metallized laminated film of the present invention includes all methods of extrusion laminating an olefin resin on a metallized film, specifically, single extrusion lamination, tandem extrusion lamination,
Coextrusion lamination, sandwich extrusion lamination with other substrates, etc. are applicable. In addition, in the present invention, the thickness of the olefin resin extrusion laminated onto the metallized film is as follows:
The thickness is preferably 3 to 200μ, more preferably 5 to 50μ. If it is less than 3μ, the suitability for laminating will be poor.
Moreover, if it exceeds 200μ, cracks are likely to occur in the vapor deposited film of the metal vapor deposited film. (E) Function The method for producing a metal vapor-deposited laminated film of the present invention includes:
Olefin resin is extruded and laminated onto a metal-deposited resin film from the extruder die to the resin temperature.
Since it is extruded at 150 to 290°C to form a molten thin film, it is possible to eliminate the occurrence of cracks in the side-deposited film of the metallized film and to prevent a decrease in the adhesive strength between the film to be deposited and the deposited film. Furthermore, since the molten thin film is treated with ozone and then pressure laminated onto the metallized film, the adhesive strength between the metallized film and the laminate layer can be excellent. (f) Examples Example 1 One side of a biaxially stretched polypropylene film having a thickness of 20 μm was subjected to a corona discharge treatment, and aluminum was deposited to a thickness of about 500 Å on the treated surface by a vacuum evaporation method to obtain a metal-deposited film. On the other hand, melt flow rate 14g/10min, density
0.918g/ ^cm3 low density polyethylene, diameter 90mm
Using an ^extruder of Thin film width melting air
One side of the molten thin film was treated with ozone by spraying at a rate of 25/min over 500 mm. Subsequently, using an extrusion laminating apparatus, the molten thin film was laminated with a pressure roll onto the vapor deposition surface of the aluminum vapor-deposited film, using the ozone-treated surface as an adhesive surface, to produce a metal vapor-deposited laminated film. At this time, set the lamination speed to 100
m/min, and the laminate layer thickness was 20μ. Regarding the obtained metal vapor-deposited laminated film, the presence or absence of cracks in the vapor-deposited film, oxygen permeability, and
The adhesive strength between the vapor deposited film and the laminate layer was measured, and the results are shown in the table. Comparative Example 1 One side of a biaxially stretched polypropylene film with a thickness of 20 μm was subjected to corona discharge treatment, and aluminum was deposited on the treated surface to a thickness of about 500 Å using a vacuum evaporation method to form a metal deposited film, and a polyester anchor coat was applied to the deposited surface. The coating amount after drying the solvent (manufactured by Toyo Morton Co., Ltd., two-component type "AD503, CAT10")
It was applied at a concentration of 0.1 g/m ² . On the other hand, melt flow rate 14g/10min, density
0.918g/ ^cm3 low density polyethylene, diameter 90mm
Using an ^extruder of Thin film width melting air
One side of the molten thin film was treated with ozone by spraying at a rate of 25/min over 500 mm. Subsequently, using an extrusion laminating device, the molten thin film was laminated with a pressure roll onto the anchor coating agent surface of the aluminum vapor-deposited film, using the ozone-treated surface as the adhesive surface, to produce a metal vapor-deposited laminated film. The lamination speed at this time was 100 m/min, and the lamination layer thickness was 20 μm. Regarding the obtained metal vapor-deposited laminated film, the presence or absence of cracks in the vapor-deposited film, oxygen permeability, and
The adhesive strength between the vapor deposited film and the laminate layer was measured, and the results are shown in the table. Examples 2 to 4, Comparative Examples 2 to 3 The procedure was the same as in Example 1 or Comparative Example 1, except that the olefin resin to be extruded and laminated, the resin temperature, the laminated layer thickness, and the ozone treatment conditions were variously changed as shown in the table. A metal vapor-deposited laminated film was produced. Reference example One side of a biaxially stretched polypropylene film with a thickness of 20μ is treated with corona discharge, and the treated side is coated with Toyo Morton's polyurethane adhesive “Adcoat”.
A mixture of “AD585” and hardener is applied at a solids rate of 2 g/m ² and then the adhesive surface is coated with a wall thickness.
A 7μ aluminum foil was laminated. Next, a polyester anchor coating agent (manufactured by Toyo Morton Co., Ltd., two-component type "AD503, CAT10") was applied to the aluminum foil surface in an amount of 0.1 after drying with the solvent.
It was applied so that it became g/ ^m2 . On the other hand, melt flow rate 14g/10min, density
0.918g/ ^cm3 low density polyethylene, diameter 90mm
Using an ^extruder of Thin film width melting air
One side of the molten thin film was treated with ozone by spraying at a rate of 8/min over 500 mm. Subsequently, using an extrusion laminating device, the molten thin film is laminated with a pressure roll on the anchor coat treated surface of the aluminum foil laminated film with the ozone treated surface as the adhesive surface.
An aluminum foil laminated film was manufactured. The laminating speed at this time was 100 m/min, and the laminated layer thickness was 20 μm. Regarding the obtained aluminum foil laminated film, the presence or absence of cracks, oxygen permeability, and
The adhesive strength between the aluminum foil and the laminate layer was measured. The results are shown in Table 1.

【table】

【table】

[Table] Application Example 1, Comparative Application Example 1 Using the metal vapor-deposited laminated film obtained in Example 1 (Application Example 1) and the aluminum foil laminated film obtained in Reference Example (Comparative Application Example), the results were obtained after bending treatment using a gelbo tester. The physical properties of the laminated film were evaluated. The gelbo tester was a device that complied with the US military standard MIL B 131, and the processing conditions were: laminated film sample piece 8 x 12 inches, test speed 40 cycles/min, motion direction 400° x 3.5 inches, 100 test cycles. The presence or absence of pinholes in the laminated film after bending treatment can be determined by placing the laminated film after treatment on a white filter paper, applying ethyl alcohol colored with methylene blue to the laminated film, and checking the presence or absence of colored spots on the filter paper. evaluated. In addition, the oxygen permeability of the laminated film after the bending treatment was evaluated. The results are shown in Table 2.

[Table] (G) Effects of the Invention The present invention has excellent adhesive strength between the metallized film and the extruded laminate layer.
To provide a method for producing a packaging material that has an extremely industrially significant effect of obtaining a metal-deposited laminated film that does not cause cracks in the deposited film and does not reduce the adhesive strength between the deposited film and the deposited film. It is. Furthermore, in the production of this packaging material, an anchor coating agent is not required between the metal vapor deposited layer and the extruded molten thin film, so it has the advantage of providing a good working environment.

Claims (1)

[Claims] 1. In producing a metal-deposited laminated film by extrusion laminating an olefin-based resin onto a metal-deposited resin film with a thickness of 100 to 1000 angstroms, the olefin-based resin is extruded from an extruder die at a resin temperature of 150 to 290°C. A method for producing a metal vapor-deposited laminated film, which comprises the steps of: forming a molten thin film, then treating the molten thin film with ozone, and then pressure laminating the metal surface of a metal-deposited resin film without using an anchor coating agent.