JP2013142161A - Method of manufacturing vapor-deposited film and laminate packaging material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a vapor-deposited film having adhesion even when a hot water treatment such as boiling sterilization or retort sterilization is performed thereon.SOLUTION: In the method of manufacturing the vapor-deposited film including the steps of performing a plasma processing by a planar magnetron type plasma processing electrode while continuously running a base film and subsequently forming a vapor-deposited layer, at a traveling position of the base film immediately above the plasma processing electrode, the maximum value of a magnetic flux density parallel to a surface of the plasma processing electrode and also parallel to a film traveling direction measured along the traveling direction of the film at an optional position in a film width direction of the base film is 20-100 mT. The base film surface is plasma processed with a plasma processing strength of 10-20 Wmin/m, and then the vapor-deposited layer is formed.

Description

  TECHNICAL FIELD The present invention relates to a method for producing a vapor deposition film used for packaging applications, and in particular, vapor deposition when heat treatment such as boil sterilization, boil cooking, retort sterilization, retort cooking, etc. is performed after being laminated with a sealant film to form a bag. The present invention relates to a method for producing a vapor-deposited film excellent in adhesion between a layer and a base film, and a laminated packaging material.

  A film obtained by vapor-depositing a metal or metal oxide on a polymer film is widely used as a packaging material because of its beautiful metallic luster, transparency and gas barrier performance.

  By the way, simply depositing metal or metal oxide on the substrate film does not provide sufficient adhesion between the substrate film and the deposition layer, and as a treatment method for improving the adhesion of the deposition layer, the substrate film The formation of an anchor deposition layer of a metal such as copper is performed under vacuum and glow discharge (Patent Document 1), and a deposition thin film made of a glow discharge treatment and a metal or a metal compound is provided on the surface of the base film ( Patent Document 2), forming a metal anchor deposition layer on the surface of the base film under glow discharge (Patent Document 3), forming a metal anchor layer on the base film under glow discharge, and forming a metal oxide layer After that, a method of providing a two-component curable resin layer having a glass transition point of 50 to 80 ° C. (Patent Document 4), forming a cored metal deposition layer on a nylon film under plasma discharge (patent text) 5), providing a pretreatment layer by reactive ion etching utilizing plasma (RIE) in the polylactic acid film surface (Patent Document 6) are known.

  Among these methods, in the method of improving adhesion by forming an anchor deposition layer of a metal such as copper on a base film under glow discharge, for example, a polymer film, an adhesive, a deposition film, an adhesive In the structure in which the sealant films are laminated in this order and the vapor deposition layer of the vapor deposition film is on the polymer film side, the water wet adhesion before and after the boil treatment between the polymer film and the vapor deposition film becomes insufficient. In order to improve wet adhesion, it was necessary to reduce the film transport speed during vapor deposition and relatively increase the processing strength. The flatness of the material film deteriorated, and this caused problems such as heat loss streaks during vapor deposition.

  In addition, as a method for improving the adhesion, a method in which an anchor coat layer made of a resin is previously provided on a base film and a metal vapor deposition layer is deposited thereon is already known (for example, Patent Document 7). . However, this method has a disadvantage that a process of providing an anchor coat layer is required and the cost is increased.

JP-A-8-267642 JP-A-8-267645 JP-A-8-269689 JP 2001-162711 A JP 10-36958 A JP 2008-272967 A JP 2007-69456 A

  An object of the present invention is a method for stably producing a vapor-deposited film having excellent adhesion after being treated with hot water at 90 to 135 ° C. for 30 minutes in a vapor-deposited film having a vapor-deposited layer on a base film. Is to provide.

In order to achieve the above object, the following means have been found. That is, the present invention is a method for producing a vapor deposition film in which a substrate film is continuously run while plasma treatment is performed, and subsequently a vapor deposition layer is formed, wherein the plasma treatment is based on a planar magnetron type plasma treatment electrode. The base film is parallel to the surface of the processing electrode and is measured along the direction of travel of the base film at an arbitrary position of the base film at the travel position of the base film. The maximum value of the magnetic flux density parallel to the running direction is 20 to 100 mT, and the strength of the plasma treatment is 10 to 200 Wmin / m ^2. Is the method.

  Furthermore, it is a laminated packaging material in which another film is laminated on the vapor deposition layer side of the vapor deposition film composed of the vapor deposition layer and the base film, and when the vapor deposition layer is an aluminum layer, it is 85 to 95 ° C. for 30 minutes. After the hot water treatment, when the water wet laminate strength between the vapor deposition layer and the base film is 1 N / 15 mm or more at a peeling rate of 50 mm / min, and the vapor deposition layer is a metal oxide layer, it is 115 to 125. After the hot water treatment at 30 ° C. for 30 minutes, the laminated packaging material is characterized in that the water wet laminate strength between the vapor deposition layer and the substrate film is 1 N / 15 mm or more at a peeling rate of 50 mm / min.

  The present invention is excellent in adhesion between the vapor deposition layer and the base film, and suppresses a decrease in adhesion when heat treatment such as boil sterilization, boil cooking, retort sterilization, and retort cooking is performed after bag making. Can be produced with good productivity.

It is sectional drawing which shows typically the relationship between the plasma processing electrode observed from the side surface of the drive | working base film, and the base film which runs. It is a figure which shows typically the relationship between a Gauss meter and a plasma processing electrode in the case of measuring a parallel magnetic flux density with a Gauss meter.

  Next, the present invention will be described in detail.

  In the present invention, examples of the base film include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films, polystyrene films, polyamide films, polycarbonate films, polyacrylonitrile films, and polyimide films. Can do. In the present invention, the base film is preferably a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) in view of chemical stability and thermal stability.

  These base films may be stretched or unstretched, but those having mechanical strength and dimensional stability are preferred. In the present invention, a polyethylene terephthalate film stretched in the biaxial direction is more preferably used as the base film.

  The present invention is a method for producing a vapor deposition film in which a plasma treatment is performed by a planar magnetron type plasma treatment electrode while a substrate film is continuously run, and a vapor deposition layer is subsequently formed. A planar magnetron type plasma processing electrode is a magnet on the back side of a planar (flat plate) plasma processing electrode so that a magnetic field is generated on the surface of the electrode, and electrons in the plasma follow the magnetic field. It is based on a system that maintains a steady discharge (magnetron plasma) by performing cycloid motion or trochoidal motion in the form of wrapping around magnetic field lines by Lorentz force. The magnet should be designed so that it can circulate around the electrode surface while drifting while the electrons are wrapped around the lines of magnetic force, for example, by arranging an S pole at the center and an N pole of the corresponding strength around it. It is preferable that strong plasma can be generated along a loop-like path around which the electrons can circulate. Depending on the shape of the electrode, the region where the strong plasma is generated has a donut shape, an elliptical shape or a long rectangular shape.

  The discharge used in the present invention preferably supplies a specific gas to a space including a planar magnetron type plasma processing electrode and a base film under a vacuum of 0.1 to 100 Pa, and the electrode (cathode) Discharge between anodes (earth). A stable discharge can be obtained by setting the pressure to 0.1 Pa or more. Moreover, plasma processing can be performed efficiently by setting it as 100 Pa or less. More preferably, it is 0.1-50 Pa, More preferably, it is 0.1-20 Pa.

  The specific gas is selected according to the purpose of the plasma treatment, but is preferably at least one selected from oxygen, nitrogen, argon, helium and water vapor, or a mixed gas thereof, more preferably oxygen, nitrogen. Or a mixed gas thereof.

  In the present invention, the magnetic flux density that is directly above the plasma processing electrode and parallel to the surface of the plasma processing electrode and parallel to the traveling direction of the film is important at the traveling position of the base film. The magnetic flux density parallel to the plasma surface treatment electrode at the travel position of the base film and parallel to the travel direction of the film is the measurement surface of the sensor for measuring the magnetic flux in the plane corresponding to the position where the base film travels. Is a magnetic flux density measured perpendicularly to the plasma processing electrode and perpendicular to the running direction of the film. The magnetic flux density has a strong and weak distribution in the film running plane directly above the plasma treatment electrode, but it is important that the maximum value measured along the running direction of the film at an arbitrary position in the width direction of the film is 20 to 100 mT. is there. When it is smaller than 20 mT, the surface treatment energy to the base film is lowered and the surface treatment becomes insufficient. Further, even if the plasma processing intensity is increased in a state where the magnetic flux density is less than 20 mT, the film is deformed by the heat generated from the plasma or the electrode surface, and this causes heat loss during vapor deposition and causes streaks.

  When it becomes larger than 100 mT, unnecessary magnetic field lines spread over a wide range, the wraparound magnetic flux increases, causing abnormal discharge, and pinholes are generated in the base film.

  Selection of the magnets described below is important for the magnetic flux density of 20 to 100 mT, and adjustment can be performed by changing a stronger magnet to increase the magnetic flux density and a weaker magnet to decrease the magnetic flux density. . Moreover, it can adjust also with the thickness of a plasma processing electrode, the thickness of the base | substrate (backing plate) which supports the plasma processing electrode demonstrated later, these magnetic permeability, and the space | interval of a plasma processing electrode and a base film.

  The magnet used for the planar magnetron electrode may be either an electromagnet or a permanent magnet, but permanent magnets such as neodymium magnets, samarium cobalt magnets, alnico magnets, barium ferrite magnets, and strontium ferrite magnets that are small and provide a strong magnetic force. Can be preferably used. Among these, neodymium magnets, samarium cobalt magnets, alnico magnets, and the like can be preferably used in terms of high magnetic flux density and strong magnetic force.

The plasma processing intensity (Wmin / m ² ) is defined as the amount of electric power (W) input to the plasma processing electrode by the film transport speed (m / min) and the width of the magnetron plasma generation region (hereinafter referred to as the plasma region width) (m). It is possible to calculate repetitive. The plasma region width of the plasma processing electrode is designed according to the width of the substrate film to be deposited, but in consideration of the uniformity of the processing strength in the width direction, the width of the substrate film is made narrower than the plasma region width. Since the plasma region at the end is designed to be removed from the travel position of the base film, it is necessary to calculate the plasma processing intensity not by the base film width but by the plasma region width. The plasma region width can be defined as the region width in which strong plasma is generated by the planar magnetron method described above, and the width in the film width direction of the strong plasma generation region in the donut shape, elliptical shape, or long rectangular shape is defined as the plasma region width. be able to. A more specific method for measuring the plasma region width is to observe the plasma state visually to confirm the plasma region having the strong shape described above, or to observe the plasma-treated electrode after discharge and to sputter with strong plasma. The width (for example, the distance between the outer peripheral portions if the erosion is a donut shape) is confirmed.

The plasma treatment intensity needs to be 10 to ²⁰⁰ Wmin / m ² . When the plasma processing strength is less than 10 Wmin / m ² , the processing strength of the base film is insufficient and the target adhesion cannot be obtained. On the other hand, if it exceeds 200 Wmin / m ² , the base film undergoes thermal deformation, which causes heat loss streaks during vapor deposition, and the target metallic luster caused by sputtering a large amount of the plasma processing electrode material. Is not obtained or the transparency of the transparent vapor-deposited layer is hindered.

  It is preferable that the conveyance speed of a base film is 200-1000 m / min. By setting it to 200 m / min or more, a vapor deposition film can be manufactured at high speed with high productivity. The practical upper limit is 1000 m / min due to the transport of the base film in vacuum and the limitation of the exhaust capability. From the viewpoint of cost, it is preferably 300 to 1000 m / min, and more preferably 400 to 1000 m / min.

  The power source for the plasma treatment is preferably an alternating current having a frequency of 1 k to 1000 kHz or a pulse wave, and it is particularly preferable to use a pulse wave power source because abnormal discharge can be easily suppressed. The frequency is more preferably 10 k to 800 kHz, still more preferably 30 k to 500 kHz. When the frequency is lower than 1000 kHz, a special matching circuit is not required, and the collision efficiency of the ions existing in the plasma and affecting the surface treatment of the base film can be kept high. Surface treatment can be performed efficiently. Moreover, by setting it as 1 kHz or more alternating current, abnormal discharge can be suppressed, the ion in plasma can be localized in the film vicinity, and the surface treatment of a base film can be performed efficiently.

  The material of the planar magnetron electrode is preferably a non-magnetic metal material such as copper, chromium, tin, silver, gold, titanium, etc., because a strong magnetic field can be generated on the electrode surface. If so, it is possible to increase the efficiency of the plasma treatment, and it is more preferable because the electrode material is inexpensive.

  The distance between the plasma treatment electrode and the base film in the present invention is preferably 5 to 20 mm. When it is 5 mm or more, there is no concern that scratches will occur due to contact with the electrode when the base film is transported, and it is less susceptible to thermal radiation from the surface of the plasma-treated electrode when a strong treatment is performed. Therefore, it is preferable. By setting it to 20 mm or less, the substrate film surface can be subjected to sufficiently powerful plasma treatment. The distance between the plasma processing electrode and the base film is more preferably 5 to 15 mm, and still more preferably 5 to 10 mm.

  Next, a vapor deposition layer is formed. The deposited layer is preferably at least one of aluminum, aluminum oxide, silicon oxide, or a mixture thereof.

  As a deposition method of the deposition layer, for example, a known method such as a vacuum deposition method, an ion plating method, a sputtering method, or an ion beam method is used. In particular, from the viewpoint of productivity, it is preferable to use a vacuum vapor deposition method or a reactive vapor deposition method for the purpose of producing a vapor deposition film with high productivity and high speed in the present invention.

  It is preferable that the average film thickness of a vapor deposition layer is 5-100 nm. By setting the thickness to 5 nm or more, a uniform vapor deposition layer can be obtained, and sufficient gas barrier performance can be ensured. Further, by setting the thickness to 100 nm or less, sufficient gas barrier performance and metallic luster can be obtained, and deterioration of gas barrier performance due to generation of cracks in the deposited layer can be suppressed. The average film thickness of the vapor deposition layer is preferably in the range of 8 to 50 nm.

  A printing layer may be provided on the vapor deposition layer. The print layer is formed to display character information, a pattern, and the like necessary for the package. For the printing layer, for example, various pigments and additives such as plasticizers, desiccants, stabilizers, etc. are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, and rubber. It is a layer comprised by the ink which consists of. As a method for forming the printing layer, for example, a known printing method such as an offset printing method, a gravure printing method, a silk screen printing method, or a known coating method such as a roll coating, a knife edge coating, or a gravure coating can be used. . The dry film thickness (solid content) of the printing layer is preferably 0.1 to 2.0 μm.

  The vapor deposition film produced by the production method of the present invention is used as a laminated packaging material by laminating another film on the vapor deposition layer side of the vapor deposition film. Specifically, a polymer film, an adhesive, a laminate in which the deposited film, adhesive, and sealant film in the present invention are laminated in this order, or a deposited film, an adhesive, a polymer film, an adhesive in the present invention, The laminate can be used in a configuration in which the sealant films are laminated in this order, or a laminate in which the vapor deposition film, the adhesive, and the sealant film in the present invention are laminated in this order.

  More specifically, when the vapor deposition film in the present invention is an aluminum layer / PET film, PET film (other film) / adhesive / aluminum layer / PET film / adhesive / unstretched polypropylene film, unstretched polyethylene A structure such as a film (other film) / adhesive / aluminum layer / PET film is employed. In the case of these aluminum vapor deposition films, the temperature at which the hot water treatment is performed needs to be 85 to 95 ° C. If it is less than 85 ° C., the effect of sterilization is small. If the treatment is performed at a temperature exceeding 95 ° C., the aluminum layer is oxidized or hydroxylated to become transparent, and the metallic luster disappears. The standard temperature for the hot water treatment is 30 minutes, but conditions are set in accordance with the purpose within a range of 15 to 60 minutes.

  When the vapor deposition film in the present invention is an aluminum oxide layer / PET film, unstretched polypropylene film / adhesive / aluminum oxide layer / PET film, unstretched polypropylene film / adhesive / stretched nylon film (other films) / adhesion A composition such as an agent / aluminum oxide layer / PET film is employed. In the case of these aluminum oxide vapor-deposited films, the temperature at which the hot water treatment is performed can be so-called retort treatment at a high temperature of 115 to 135 ° C. If it is less than 115 degreeC, the effect of retort sterilization is small, and if it processes at the temperature exceeding 135 degreeC, a deformation | transformation of a laminated packaging material will arise. The standard temperature for the hot water treatment is 30 minutes, but conditions are set in accordance with the purpose within a range of 15 to 60 minutes. Instead of aluminum oxide, silicon oxide or a mixture of aluminum oxide and silicon oxide may be used.

  A sealant film is provided so that it may become a heat sealing | fusion layer, when forming a bag-shaped package. For example, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid ester copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer and their It is formed of a heat-fusible resin such as a metal cross-linked product. The thickness of the sealant film is determined according to the purpose, but is generally in the range of 15 to 200 μm. As a method for forming the sealant film, it is common to use a dry laminating method in which a film-like material made of the above resin is bonded using an adhesive such as a two-component curable urethane resin. It is also possible to laminate by a method. The sealant film used for the hot water treatment at 85 to 95 ° C. can be either a polypropylene film or a polyethylene film, but the sealant film used for the retort treatment at 115 to 135 ° C. is polypropylene from the viewpoint of heat resistance. A film is preferred.

  In order to ensure the bag breaking strength and puncture strength required as packaging materials, a polymer film may be provided on the opposite side of the vapor-deposited film from the side to be bonded to the sealant film, or between the sealant film and the Examples of the molecular film include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films, polystyrene films, polyamide films, polycarbonate films, polyacrylonitrile films, and polyimide films. In the present invention, the polymer film is preferably composed of a biaxially stretched nylon film, a biaxially stretched polyethylene terephthalate film, or a biaxially stretched polypropylene film from the viewpoint of mechanical strength and thermal stability.

  The deposited film in the present invention in the above laminate is treated with hot water at 85 to 95 ° C. when the deposited layer is an aluminum layer and with hot water at 115 to 135 ° C. when the deposited layer is a metal oxide layer for 30 minutes. The water wet laminate strength is preferably 1 N / 15 mm or more, more preferably 2 N / 15 mm or more. The water-wet laminate strength refers to the peel strength when measured by low-speed peeling at 50 mm / min by T-type peeling while continuously supplying water to the peeling portion. Usually, the laminate strength is measured at a peel strength of 150 to 300 mm / min, but this peel evaluation method is a slow speed of 50 mm / min and peels while supplying water to the peeled portion. is there.

  By using the vapor deposition film manufactured in the present invention, for example, a polymer film, an adhesive, a vapor deposition film, an adhesive, and a sealant film are laminated in this order, and the vapor deposition layer of the vapor deposition film is on the polymer film side. The water-wet laminate strength after treatment for 30 minutes with hot water at 90 ° C. to 135 ° C. between the film and the deposited film can be 1 N / 15 mm or more. That is, the base film and the vapor deposition layer are densely and firmly adhered by the plasma treatment, so that the base film and the vapor deposition layer maintain sufficient adhesion even after the boil treatment or the retort treatment.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical property in an Example and a comparative example was measured as follows.

(1) Creation of laminated body Hereinafter, the laminated packaging material in the present invention is exemplified, but the present invention is not limited by these illustrations.

A. Laminate 1
The vapor deposition surface of the vapor deposition film in the present invention is coated with a urethane type two-component adhesive (AD503, CAT-10 manufactured by Toyo Morton Co., Ltd.) with a dry film thickness equivalent to 3 μm, and a 12 μm PET film (manufactured by Toray Industries, Inc.). Laminate the “Lumirror” P60) side facing the vapor deposition surface, and then apply the same urethane-based two-component adhesive on the side of the base film opposite to the vapor deposition surface to a dry film thickness equivalent to 3 μm. Laminated with unstretched PP film ("Torayfan" NO "ZK100" manufactured by Toray Film Processing Co., Ltd.) and aged for 48 hours in an atmosphere of 40 ° C, PET film, vapor deposition film of the present invention and It was set as the laminated body 1 of the 3 layer structure which laminated the extending | stretched PP film.

B. Laminate 2
On the vapor deposition surface of the vapor deposition film according to the present invention, a urethane-based two-component adhesive is applied in a dry film thickness equivalent to 3 μm, and on the corona treatment surface side of a 15 μm nylon film (“Emblem” ONUM manufactured by Unitika Ltd.) Laminate with the vapor-deposited surface facing, and then apply the same urethane-based two-component adhesive on the nylon film side opposite to the corona-treated surface to the equivalent of 3 μm, and then apply a 60 μm unstretched PP film (Toray Film Processing Co., Ltd.) Laminated product made by laminating “Trephan” NO “ZK100”) and aged for 48 hours in a 40 ° C. atmosphere, and laminating the deposited film, nylon film and unstretched PP film in the present invention. 2.

C. Laminate 3
Corona-treated surface of 50 μm low density polyethylene film (“TUX” HZ manufactured by Tosero Co., Ltd.) coated with 3 μm of urethane-based two-component adhesive on the vapor deposition surface of the vapor deposition film in the present invention. The laminate 3 was laminated with the vapor-deposited surface facing it, and aged for 48 hours in a 40 ° C. atmosphere to obtain a laminate 3 having a two-layer structure in which the vapor-deposited film and the low-density polyethylene film of the present invention were laminated.

(2) Laminate strength before hot water treatment (N / 15mm)
The measuring method of the lamination strength before a hot water process is shown. Cut the laminate produced in (1) above into a 15mm width x 200mm length, and use a "Tensilon" universal testing machine manufactured by Orientec Co., Ltd. The peel strength before hot water treatment was measured under a pulling condition of 50 mm / min.
1N / 15 mm or more was determined to be a level with good laminate strength.

(3) Laminate strength after hot water treatment (N / 15mm)
In the same manner as the laminate strength measurement sample before the hot water treatment, the laminated laminate is cut into 12 cm square. Two sheets of sealant film are placed on the inside, and three sides are sealed using Fuji Impulse Co., Ltd. Impas Sealer “VAC-PAC” VT-400 under the conditions of heating for 2 seconds and cooling for 3 seconds. 100 ml of distilled water is put into the bag-like place, and the open part is sealed so that air does not enter and sealed. Put this sample in a retort food autoclave manufactured by Tommy Seiko Co., Ltd., leave it in hot water for 30 minutes at the set temperature, then take it out and immerse it in room temperature water to confirm that it reaches room temperature. The seal part was cut, the water inside the bag was discharged, and the laminate strength after the hot water treatment was measured under the same conditions as the laminate strength measurement before the hot water treatment.
1 N / 15 mm or more was determined to be a level of good laminate strength after hot water treatment.
(4) Film appearance The vapor deposition surface of the vapor deposition film according to the present invention is visually observed, ○ for heat loss and no scratches, △ for scratches, but for practical use, Δ for heat loss, scratches, and pinholes. X was not able to endure the resistance to the subsequent process of laminating.
(5) Measuring method of parallel magnetic flux density (mT) The measuring method of a parallel magnetic flux density is demonstrated using FIG. 1 and FIG.
FIG. 1 is a cross-sectional view showing the relationship between a plasma processing electrode observed from the side of a traveling substrate film and the traveling substrate film. The plasma processing electrode 2 is connected to a copper plate that is water-cooled from behind called a backing plate by indium solder or the like. The lines of magnetic force 7 emitted from the magnet 5 under the backing plate 3 pass through the backing plate 3 and the plasma processing electrode 2 and reach the vicinity of the film.
Using a Gauss meter (model GM-301) manufactured by Nippon Magnetic Industry Co., Ltd., the magnetic flux density immediately above the plasma treated electrode, parallel to the electrode, and parallel to the film running direction was measured as follows. First, the distance between the plasma processing electrode 2 and the base film 6 is measured with a non-magnetic scale. The measurement detector 10 of the gauss meter is held perpendicularly to the plasma processing electrode 2 while keeping the above distance while applying the scale, and the measurement detector 10 is further directed perpendicularly to the film running direction. In this state, the maximum value of the magnetic flux density was read from the indicated value of the gauss meter while moving on the plasma processing electrode at a speed of 1 to 2 cm / second in the film running direction (11 direction). The width direction (12 at the position of the substrate film, that is, the position satisfying the distance between the plasma treatment electrode and the substrate film and corresponding to the width of the substrate film (the position outside the width of the substrate film is not measured) The minimum value and the maximum value were obtained from the parallel magnetic flux density maximum value data acquired in 1 cm increments, and it was confirmed whether both the minimum value and the maximum value were within the range of 20 to 100 mT.

[Example 1]
As a base film, a PET film having a thickness of 12 μm (“Lumirror” P60 manufactured by Toray Industries, Inc.) was used, and plasma treatment and subsequent vapor deposition were performed in an ordinary roll-to-roll type vapor deposition machine. A neodymium magnet (N40 manufactured by Neomag Co., Ltd.) is installed on the back side of the planar magnetron type plasma processing electrode (material: copper, plasma generation region width: 2 m), and the distance between the plasma processing electrode and the base film is 10 mm. Magnetic flux density parallel to the electrode surface and film running direction (hereinafter referred to as parallel magnetic flux density) at the running position of the material film (base film width: 1.8 m) is a minimum value of 28 mT and a maximum value of 33 mT (hereinafter referred to as 28 to 33 mT). It was confirmed that AC power with a film conveyance speed of 400 m / min, a pressure of 0.4 Pa using oxygen gas as the discharge gas, a frequency of 50 kHz and a power input of 32 kW for the plasma processing electrode (power source: “TruPlasma” MF3040 manufactured by Hüttinger) Then, plasma treatment was performed at a treatment intensity of 40 Wmin / m ² , and a 50 nm aluminum vapor deposition layer was continuously formed in the same vacuum chamber under a vacuum of 0.013 Pa without releasing the vacuum. The laminated body 1 was produced using this vapor deposition film.

[Example 2]
The same plasma treatment electrode as in Example 1 was used, the magnet was changed to an Alnico magnet (SAN52 manufactured by Neomag Co., Ltd.), the distance between the plasma treatment electrode and the substrate film was 5 mm, and the parallel magnetic flux density was 90 to 100 mT. A PEN film with a thickness of 12 μm (“Teonex” Q51 manufactured by Teijin DuPont Films Ltd.) is used as the base film, the film conveyance speed is set to 450 m / min, nitrogen gas is used as the discharge gas, and the plasma is applied under a vacuum of 20 Pa. A deposited film in which AC power (power source: “TruPlasma” MF7200) manufactured by Hüttinger, Germany) is applied to the processing electrode, plasma processing is performed at a processing strength of 200 Wmin / m ² , and an aluminum oxide vapor deposition layer is formed to 6 nm. The laminated body 2 was produced.

[Example 3]
The base film is a 25 μm-thick polypropylene film (“Torphan” YT42 manufactured by Toray Industries, Inc.), a samarium cobalt magnet (SS30M manufactured by Neomag Co., Ltd.) is used as the magnet, and the distance between the plasma-treated electrode and the base film Is 10 mm (base film width: 0.25 m, plasma generation region width: 0.3 m), parallel magnetic flux density is 20 to 25 mT, film transport speed is 300 m / min, and argon gas is used as the discharge gas and a vacuum of 0.1 Pa. The plasma treatment electrode was subjected to plasma treatment with an applied power of 3 kW and a frequency of 280 kHz (power source: Astech Co., Ltd. LG-30S) at a treatment intensity of 33 Wmin / m ² to form a silicon oxide layer of 20 nm. The laminated body 2 was produced with the vapor deposition film.

[Example 4]
The same plasma-treated electrode as in Example 3 was used, and the magnet was changed to an Alnico magnet (SAN52 manufactured by Neomag Co., Ltd.), the distance between the plasma-treated electrode and the base film was 15 mm, and the parallel magnetic flux density was 70 to 80 mT. Using a 15 μm thick nylon film (“Emblem” ONUM made by Unitika Co., Ltd.) as the base film, using a carbon monoxide gas as the discharge gas at a vacuum of 50 Pa and using a carbon monoxide gas as the discharge gas, the input power is 3 kW. Then, AC power having a frequency of 1000 kHz was applied (power source: LG-30S manufactured by Astec Co., Ltd.), plasma treatment was performed at a treatment strength of 40 Wmin / m ² , and a laminate 3 was produced using a vapor deposition film in which an aluminum vapor deposition layer was formed to 40 nm. .

[Example 5]
The substrate film is a PET film with a thickness of 12 μm (“Lumirror” P60 manufactured by Toray Industries, Inc.), a samarium cobalt magnet (Neomag Corp. SS30M) is used as the magnet, and the distance between the plasma-treated electrode and the substrate film is 15 mm. (Base film width: 2.2 m, plasma generation region width: 2.4 m) Parallel magnetic flux density is 46 to 55 mT, film transport speed is 200 m / min, carbon dioxide gas is used as discharge gas, and vacuum is applied at 100 Pa. It is a vapor deposition film in which a pulse power of 5 kW and a frequency of 1 kHz is applied (power source: “TruPlasma” Bipolar 4030 manufactured by Hüttinger, Germany), plasma treatment is performed so that the treatment strength is 10 Wmin / m ² , and an aluminum deposition layer is formed to 95 nm. The laminated body 1 was produced.

[Example 6]
Using the same plasma-treated electrode as in Example 1, the magnet was changed to a ferrite magnet (Neomag Y8T), the parallel magnetic flux density was 21 to 25 mT, the film transport speed was 400 m / min, and oxygen gas was used as the discharge gas. under a vacuum of .5Pa, input power 20 kW, the frequency 0.8kHz pulsed power (power: Germany Hyu' Tinga over company "TruPlasma" Bipolar4030), a vapor-deposited aluminum layer using a vapor deposition film was 50nm form a treated intensity as 25Wmin / ^{m 2} Thus, a laminate 1 was produced.
Although the power supply frequency was slightly low and abnormal discharge was observed at a frequency of about once per minute during processing, it was not at a level causing quality problems, and the wet wet laminate strength was low, but there was no practical problem.

[Example 7]
Using a 25 μm-thick polypropylene film (“Torphan” YT42 manufactured by Toray Industries, Inc.) as the base film and a neodymium magnet (N40 manufactured by Neomag Co.) as the magnet, the distance between the plasma-treated electrode and the base film is 3 mm (base film width: 0.12 m, plasma generation region width: 0.15 m), the parallel magnetic flux density is 75 to 85 mT, the film conveyance speed is 300 m / min, the discharge gas is nitrogen gas, and the vacuum is 20 Pa. The laminated body 3 was produced using the vapor deposition film which formed the aluminum vapor deposition layer with 110 nm as process intensity | strength 67Wmin / m < ² > by applying AC power of input power 3kW and frequency 1050kHz (power supply: LG-30S by Astec Co., Ltd.). .
Although the power supply frequency was slightly higher and the water wet laminate strength was lower, there was no practical problem. In addition, the distance between the electrode and the film was as narrow as 3 mm, and a slight scratch was observed at the end.

[Example 8]
Using a 15 μm thick nylon film (“Emblem” ONUM made by Unitika Co., Ltd.) as the base film and a ferrite magnet (Y8T made by Neomag Co., Ltd.) as the magnet, the distance between the plasma-treated electrode and the base film is 4 mm. (Base film width: 0.8 m, plasma generation region width: 1 m), parallel magnetic flux density is 25 to 30 mT, film transport speed is 250 m / min, carbon monoxide gas is used as the discharge gas, and vacuum is 0.09 Pa. Then, a pulsed power of 10 kW and a frequency of 150 kHz was applied (power source: Hokko Co., Ltd. “EnePulse” 10 LV), the processing strength was 40 Wmin / m ² , and a laminate 2 using a vapor deposition film in which a silicon oxide vapor deposition layer was formed to 10 nm. Was made.
Although the pressure during the plasma treatment was slightly lower and the discharge tended to be unstable, it was not a problem level.

[Example 9]
Using the same plasma-treated electrode as in Example 2, a laminate 2 was produced with a vapor deposition film in which an aluminum oxide vapor deposition layer was formed at 6 nm under a vacuum of 110 Pa with an input power of 50 kW and a treatment strength of 56 Wmin / m ² .
Although the pressure during the plasma treatment was slightly higher and the water wet laminate strength was lower, there was no practical problem.

[Comparative Example 1]
In Example 6, the input power was changed to 7 kW, the processing strength was 9 Wmin / m ² , and the laminate 1 was produced using a vapor deposition film in which an aluminum vapor deposition layer was formed to 50 nm.

[Comparative Example 2]
A polypropylene film having a thickness of 25 μm (“Torphan” YT42 manufactured by Toray Industries, Inc.) is used as the base film, and the distance between the plasma processing electrode and the base film is 3 mm (base film width: 0.25 m, plasma generation region width) : 0.28 m), a parallel magnetic flux density of 75 to 82 mT, a film conveyance speed of 300 m / min, a nitrogen gas as a discharge gas, a 20 Pa vacuum, and an AC power of 18 kW and a frequency of 50 kHz are applied (power supply) : Huttinger “TruPlasma” MF7200, Germany), with a processing strength of 214 Wmin / m ² , a deposited film with an aluminum deposited layer of 110 nm was produced. However, the heat loss was severe and processing into a laminate was abandoned.

[Comparative Example 3]
Using a nylon film with a thickness of 15 μm ("Emblem" ONUM made by Unitika Co., Ltd.) as the base film and a ferrite magnet (Y8T made by Neomag Co., Ltd.) as the magnet, the distance between the plasma-treated electrode and the base film is set 4 mm (base film width: 1.8 m, plasma generation region width: 2 m), parallel magnetic flux density is 15 to 18 mT, film transport speed is 180 m / min, carbon monoxide gas is used as the discharge gas, and vacuum is 0.13 Pa Below, a pulsed power of 10 kW input power and a frequency of 150 kHz was applied (power source: “EnePulse” 10 LV manufactured by Hokko Co., Ltd.), the processing strength was 28 Wmin / m ² , and a deposited film in which a silicon oxide deposited layer was formed to 10 nm was used. The laminated body 2 was produced.

[Comparative Example 4]
Using a 12 μm thick PET film (“Lumirror” P60 manufactured by Toray Industries, Inc.) as the base film, and using a neodymium magnet (N40 manufactured by Neomag Co., Ltd.) as the magnet, the distance between the plasma-treated electrode and the base film is determined. 4 mm (base film width: 0.09 m, plasma generation region width: 0.1 m), parallel magnetic flux density is 105 to 120 mT, film transport speed is 350 m / min, and nitrogen gas is used as a discharge gas under a vacuum of 75 Pa. Then, AC power with a power input of 5 kW and a frequency of 350 kHz was applied (power source: Astech Co., Ltd. LG-50S), and a deposited film with an aluminum deposited layer of 120 nm was formed with a treatment strength of 143 Wmin / m ^2. Since there were many pinholes and so on, we gave up processing the laminate.

  A summary is shown in Tables 1-3. As is clear from Tables 1 to 3, the deposited films obtained in Examples 1 to 9 had no major problem in appearance, and the water wet laminate strength before and after the hot water treatment was at a sufficient level. In Comparative Examples 1 to 4, there were problems such as insufficient wet laminate strength and poor appearance.

1: Cathode case 2: Plasma processing electrode 3: Backing plate 4: Anode (ground)
5: Magnet 6: Base film 7: Magnetic field line 8: Discharge gas introduction nozzle 9: Gauss meter 10: Gauss meter measurement detection unit 11: Travel direction of the base film 12: Direction perpendicular to the travel direction of the base film

Claims (5)

A method for producing a vapor deposition film in which a plasma treatment is performed while continuously running a substrate film, and subsequently a vapor deposition layer is formed, wherein the plasma treatment is based on a planar magnetron plasma treatment electrode, Directly above and at the travel position of the base film, measured along the travel direction of the base film at an arbitrary position in the width direction of the base film, parallel to the treated electrode surface, and the base film travel direction The manufacturing method of a vapor deposition film which forms a vapor deposition layer, after plasma-treating the surface of a base film with the intensity | strength of the magnetic flux density parallel to 1 to 20-100 mT, and the intensity | strength of this plasma treatment being 10-200 Wmin / m < ² >. The method for producing a vapor-deposited film according to claim 1, wherein the power supply frequency of the plasma treatment is an alternating current or pulse wave with a frequency of 1 k to 1000 kHz. The method for producing a deposited film according to claim 1 or 2, wherein the plasma treatment is performed under a vacuum of 0.1 to 100 Pa, and the distance between the plasma treatment electrode and the base film is 5 to 20 mm. A laminated packaging material in which another film is laminated on the vapor deposition layer side of the vapor deposition film having a vapor deposition layer and a base film, wherein the vapor deposition layer is a layer made of aluminum, and is heated at a temperature of 85 to 95 ° C. for 30 minutes. A laminated packaging material characterized in that, after water treatment, the water wet laminate strength between the vapor deposition layer and the substrate film is 1 N / 15 mm or more at a peeling rate of 50 mm / min. A laminated packaging material in which another film is laminated on the vapor deposition layer side of the vapor deposition film having the vapor deposition layer and the base film, wherein the vapor deposition layer is a layer made of a metal oxide, and a temperature of 115 to 125 ° C. for 30 minutes. After the hydrothermal treatment, a laminated packaging material characterized in that the water wet laminate strength between the vapor deposition layer and the substrate film is 1 N / 15 mm or more at a peeling rate of 50 mm / min.