JP2005131853A - Strongly bonded vapor deposition film and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a strongly bonded vapor deposition film having at least a vapor deposition layer comprising an inorganic oxide on a film base material comprising a plastic material, especially reinforced in the adhesion of the film base material and the vapor deposition layer, causing no delamination even if subjected to heat sterilization treatment, for example, retorting or boiling treatment and having gas barrier properties, and also to provide a method for production thereof. <P>SOLUTION: When producing the strongly bonded vapor deposition film by providing at least the vapor deposition layer comprising the inorganic oxide on at least one side of the film base material comprising the plastic material, plasma post-treatment using magnetron discharge is applied to the surface of the vapor deposition layer under treatment unit pressure of 8-100 Pa. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is produced by a method for producing a vapor-deposited film in which a vapor-deposited layer comprising at least an inorganic oxide is provided on a film substrate, in particular, a highly-adhesive vapor-deposited film having excellent adhesion between the film substrate and the vapor-deposited layer, and its production method. It is related with the strong adhesion vapor deposition film made.

  In recent years, packaging materials used for packaging foods, non-foods, pharmaceuticals, etc. have altered oxygen, water vapor, and other contents that permeate the packaging material in order to suppress the alteration of the contents and retain their functions and properties. It is necessary to prevent the influence of the gas to be produced, and it is required to have a gas barrier property for blocking these. Therefore, conventionally, a packaging material using a metal foil made of a metal such as aluminum, which is less affected by temperature, humidity and the like, as a gas barrier layer has been generally used.

  However, packaging materials using metal foils such as aluminum are extremely less affected by temperature, humidity, etc. and have excellent gas barrier properties, but the contents cannot be confirmed through the packaging material. In some cases, it has to be treated as an incombustible material, and a metal detector cannot be used for inspection.

  Therefore, as a packaging material that overcomes these drawbacks, silicon oxide is formed on a film substrate made of a polymer film as described in Patent Documents 1 and 2 by thin film forming means such as vacuum deposition or sputtering. A vapor deposition film in which a vapor deposition thin film made of an inorganic oxide such as aluminum oxide is formed has been developed. These vapor-deposited films are known to have transparency and gas barrier properties against oxygen, water vapor, etc., and have transparency and gas barrier properties that cannot be obtained with packaging materials having metal foil or metal foil layers. It is suitable as a material.

  However, in the above packaging material, if the film base material is provided with a vapor deposition layer made of an inorganic oxide without pretreatment, the adhesion between the film base material and the vapor deposition layer is weak. When heat sterilization treatment such as retort treatment is performed, delamination may occur.

  In order to solve this problem, in order to increase the adhesion between the film substrate and the vapor deposition layer composed of the inorganic oxide, the primer layer is previously applied on the film substrate before the formation of the inorganic oxide thin film by a coating method such as wet coating. Application and formation have been performed for a long time. However, this method has a problem that the number of steps other than the vacuum process is increased, and the working efficiency is deteriorated.

In addition, as a method of performing in-line together with the vapor deposition layer forming step in order to improve the adhesion, an attempt has been made to improve the adhesion by performing a plasma pretreatment on the film substrate. However, in this method, even if a part where the adhesion with the vapor deposition layer is poor due to incomplete plasma pretreatment, it is not possible to redo the treatment for improving the adhesion later. There is a problem that the yield deteriorates.
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017

  The present invention has been made to solve the above-mentioned problems, and is a vapor-deposited film in which a vapor-deposited layer made of at least an inorganic oxide is provided on a film base made of a plastic material, particularly a film base and a vapor-deposited layer. It is intended to provide a strongly adhered vapor-deposited film having gas barrier properties that does not generate delamination even if heat sterilization treatment such as retort / boil treatment is performed, and a method for producing the same.

  In order to achieve the above object, the invention according to claim 1 is a method for producing a vapor deposition film comprising at least one vapor deposition layer made of an inorganic oxide on at least one surface of a film substrate made of a plastic material. Then, after the vapor deposition layer is formed, a plasma post-treatment using magnetron discharge is performed on the surface thereof at a treatment unit pressure of 8 Pa to 100 Pa.

  The invention described in claim 2 is the method for producing a strongly adhered vapor deposition film according to claim 2, wherein the plasma post-treatment is treatment by ion bombardment using magnetron discharge or treatment by plasma ion shower. Features.

  Furthermore, the invention according to claim 3 is the method for producing a strong adhesion vapor deposition film according to claim 1 or 2, wherein the film substrate is made of polyethylene, polypropylene, polyamides, polyesters, polycarbonate, polyacrylonitrile, polystyrene, Containing at least one of polyvinyl chloride, cellulose, triacetyl cellulose, polyvinyl alcohol, and polyurethane as a component, or as a copolymer component, or made of a plastic material having a chemical modification thereof as a component. It is characterized by.

  Furthermore, the invention according to claim 4 is the method for producing a strong adhesion vapor deposition film according to claim 3, wherein the polyester is polyethylene terephthalate, polyethylene naphthalate, boribylene terephthalate, boribylene naphthalate and a mixture thereof. It consists of one of copolymers.

  Furthermore, the invention according to claim 5 is the method for producing a strong adhesion vapor deposition film according to any one of claims 1 to 4, wherein the vapor deposition layer is made of any one of aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. It is characterized by becoming.

  Furthermore, the invention according to claim 6 is the method for producing a strong adhesion vapor deposition film according to any one of claims 1 to 5, wherein the formation of the vapor deposition layer and the plasma post-treatment are performed in-line. Features.

  Furthermore, the invention according to claim 7 is the method for producing a strong adhesion vapor-deposited film according to any one of claims 1 to 6, wherein the water-soluble polymer and one kind are formed on the vapor-deposited layer subjected to the plasma post-treatment. It is characterized in that a gas barrier coating layer formed by applying a water-soluble or water / alcohol mixed solution containing the above metal alkoxide or a hydrolyzate thereof and drying by heating is provided.

  Furthermore, the invention according to claim 8 is the method for producing a strong adhesion vapor-deposited film according to claim 7, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. Features.

  Furthermore, the invention according to claim 9 is the method for producing a strong adhesion vapor-deposited film according to claim 7, wherein the water-soluble polymer is at least polyvinyl alcohol or poly (vinyl alcohol-co-ethylene), cellulose, and starch. It has one or more types as a component.

  Furthermore, the invention according to claim 10 is a strong adhesion vapor-deposited film produced by the method for producing a strong adhesion vapor deposition film according to any one of claims 1 to 10.

  The strong adhesion vapor-deposited film of the present invention has extremely good adhesion between a film substrate made of a plastic material and a vapor-deposited layer made of an inorganic oxide, and even when subjected to heat sterilization treatment such as retort bottle treatment. Lamination does not occur, and according to the method for producing a strongly adhered vapor-deposited film of the present invention, a strongly adhered vapor-deposited film can be produced efficiently and with a high yield.

  Hereinafter, the best embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 and FIG. 2 are cross-sectional configuration diagrams for explaining the strong adhesion vapor deposition film of the present invention. A strong adhesion vapor deposition film 10 shown in FIG. 1 is provided by laminating a vapor deposition layer 2 made of an inorganic oxide on the surface of a film substrate 1 made of a plastic material. On the other hand, the strong adhesion vapor deposition film 20 shown in FIG. 2 is provided by sequentially laminating a vapor deposition layer 12 made of an inorganic oxide and a gas barrier coating layer 3 on the surface of a film substrate 11 made of a plastic material.

  The above-described film bases 1 and 11 are made of a plastic material, and are preferably transparent if possible in order to make use of the transparency of the vapor deposition layers 1 and 12 provided on the upper surface thereof. Examples of the film substrates 1 and 11 include polyester films made of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films made of polyethylene, polypropylene, etc., polystyrene films, polyamide films, polycarbonate films, polyacrylic. A nitrile film, a polyimide film, etc. are mentioned. The film substrates 1 and 11 may be either stretched or unstretched, but those having mechanical strength and dimensional stability are preferred. Among these, a polyethylene terephthalate film or a polyamide film arbitrarily stretched in the biaxial direction is preferably used. Further, on the surface opposite to the surface on which the vapor deposition layers 2 and 12 are provided with respect to each of the film bases 1 and 11, various known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing agent, a plasticizer are provided. A layer made of an agent, a lubricant or the like may be provided.

  Although the thickness of the film bases 1 and 11 is not particularly limited, the primer layer, the vapor deposition layers 2 and 12 made of an inorganic oxide, which will be described later, and the gas barrier coating layer 13 are laminated and provided. Considering processability, the range of 3 to 200 μm is preferable for practical use, and 6 to 30 μm is particularly preferable. The structure may be a multilayer structure in which films having different properties are laminated in consideration of suitability as a packaging material.

  On the other hand, the vapor-deposited layers 2 and 12 made of an inorganic oxide are made of a vapor-deposited thin film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof. Any layer having a gas barrier property against the above may be used. In view of resistance to heat sterilization treatment such as boil / retort treatment, it is more preferable to use a vapor deposition layer made of aluminum oxide or silicon oxide. However, the vapor deposition layers 2 and 12 constituting the strong adhesion vapor deposition film of the present invention are not limited to those composed of the above-described inorganic oxides, but are vapor deposition thin films made of inorganic oxide materials that meet the above conditions. If it is.

In addition, the optimum conditions for the thicknesses of the vapor deposition layers 2 and 12 differ depending on the type and configuration of the inorganic oxide used, but in general, the thickness is preferably in the range of 5 to 300 nm, and the value is appropriately selected. However, if the thickness is less than 5 nm, a uniform film may not be obtained or the thickness may not be sufficient, and the function as a gas barrier layer may not be sufficiently achieved. In addition, when the thickness exceeds 300 nm, the thin film cannot be kept flexible, and there is a problem that the thin film may be cracked by applying an external force such as bending or pulling after the film formation. More preferably, it exists in the range of 10-150 nm.

  Furthermore, although there are various methods for forming the vapor deposition layers 2 and 12 made of inorganic oxide on the film bases 1 and 11, they may be generally formed by a normal vacuum vapor deposition method. Other thin film formation methods such as sputtering, ion plating, and plasma vapor deposition (CVD) can also be used. However, considering productivity, the vacuum deposition method is the best at present. It is preferable to use one of an electron beam heating method, a resistance heating method, and an induction heating method as a heating means of the vacuum evaporation method, but an electron beam heating method should be used in consideration of the wide selection of evaporation materials. Is more preferable. Moreover, in order to improve the adhesiveness of a vapor deposition layer and a film base material, and the denseness of a vapor deposition layer, it is also possible to vapor-deposit using a plasma assist method or an ion beam assist method. In order to increase the transparency of the vapor deposition layer, it is possible to use reactive vapor deposition performed by blowing various gases such as oxygen during vapor deposition.

  In the present invention, after the vapor deposition layers 2 and 12 made of the inorganic oxide are provided by vapor deposition, in order to improve the adhesion between the film bases 1 and 11 and the vapor deposition layers 1 and 12, magnetron discharge is applied to the surface. The used plasma post-treatment is performed at a treatment unit pressure of 8 to 100 Pa. As the plasma post-treatment method, treatment by ion bombardment using magnetron discharge or treatment by plasma ion shower is used.

  A plasma diffusion method that is generally used as a plasma treatment is a plasma ion etching method in which the configuration of the apparatus and the operation procedure are simple. However, in this method, since the sample is exposed to plasma ions, the very thin inorganic oxide deposition layer of 5 to 300 nm is damaged by the ion bombardment and the initial gas barrier property is lowered. Not applicable to post-processing. On the other hand, if processing by ion bombardment using magnetron discharge or processing by plasma ion shower is performed in a rare gas at a processing unit pressure of 8 to 100 Pa, the sample surface is subjected to plasma processing in a mild environment. It is possible to prevent the vapor deposition layer made of inorganic oxide from being damaged, and it is possible to improve the adhesion to the film substrate and to maintain the initial gas barrier property.

  When the plasma post-treatment is performed in this manner after the deposition layer made of the inorganic oxide is provided, the once-deposited inorganic oxide is ionized again by the effect of the plasma to start vibration. Due to this effect, penetration of the inorganic oxide into the surface of the film base material, which was just on the surface of the film base material immediately after deposition, occurs, and the deposited layer formed into a denser film. As a result, the adhesion between the film substrate and the vapor deposition layer made of an inorganic oxide is dramatically improved. Furthermore, this plasma post-treatment is possible in that the plasma post-treatment can be performed again even if the vapor-deposition treatment of the vapor-deposited layer made of an inorganic oxide is not performed or is insufficient due to a malfunction of the apparatus. Better than preprocessing.

  FIG. 3 and FIG. 4 show an example of a processing apparatus that performs the above-described plasma post-treatment in a winding type in-line.

The processing apparatus shown in FIG. 3 is configured such that plasma post-processing is performed by ion bombardment using magnetron discharge, and its main part is configured as a magnetron sputtering film forming unit. In this processing apparatus, a target electrode 4, a target 5 attached to the target electrode 4, and a power source 6 for applying a discharge voltage so that the target electrode 4 becomes a negative potential are provided. It is attached.
Since each unit arranged in this way forms a magnetic field along the surface of the target 5, electrons generated by the discharge cause a spiral motion in the magnetic field, and the flight distance can be extended. Opportunities for collision with the residual gas in the tank increase, and the residual gas becomes plasma, so that the density of cations increases dramatically at a low processing pressure. Accordingly, a stable plasma region having a high density can be obtained near the target even at a low voltage. At this time, the target 5 is a metal having a low sputtering rate. In this state, cations are reflected on the surface of the target, and ions are formed on the surface of the vapor deposition layer of the wound film laminate that is carried in the state where the vapor deposition layer made of an inorganic oxide is formed on the film substrate. Since it is injected, the deposited layer is not damaged.

  On the other hand, the processing apparatus shown in FIG. 4 is configured such that plasma post-treatment is performed by plasma ion shower using magnetron discharge, and similar to the above-described processing apparatus performing ion bombardment processing using magnetron discharge. However, it is different in that no magnet is used for the electrode. In this processing apparatus, a positive voltage is applied to the target electrode 4 disposed in the vicinity of the wound film laminate that is carried in a state in which a vapor deposition layer made of an inorganic oxide is formed on the film substrate. By arranging a pair of positive electrodes 8 for applying a plasma, a plasma discharge is caused between the target electrode 4 and the positive electrode 8, and the cations generated thereby are reflected on the target electrode 4, and the winding shape is A cation is irradiated in a shower-like manner on the deposited layer of the film laminate. Even in the plasma post-processing using the processing apparatus having such a configuration, desired ions can be implanted therein without damaging the deposited layer as the processing surface.

  These plasma post-treatments are performed in a dilute gas state with a treatment unit pressure of 8 to 100 Pa. When the pressure is lower than 8 Pa, the amount of cations irradiated to the vapor deposition layer made of an inorganic oxide is reduced, so that the adhesion with the film substrate cannot be improved. On the other hand, if the pressure is higher than 100 Pa, the vapor deposition layer made of an inorganic oxide is damaged by ions, and the desired gas barrier property derived from the vapor deposition layer cannot be expressed, which is not preferable. More preferably, the processing unit pressure is in the range of 9 to 30 Pa.

  As the target electrode 4 and the target 5 in each processing apparatus described above, a metal that is not sputtered by ion bombardment, for example, Fe, Cr, Ni, Ta, Mo, Al, or an alloy thereof is used.

  On the other hand, there is no limit to the number of plasma post-treatments. That is, even if the plasma post-treatment is not successfully performed on the deposited layer for some reason or is an incomplete treatment, the adhesion can be improved by performing the plasma post-treatment again. The processing time for one time is not particularly limited as long as the processing target object is not deformed by heat during processing.

  The strong adhesion vapor-deposited film of the present invention is obtained as described above, but the strong adhesion vapor-deposited film of the present invention is not limited to the one having the above-described configuration, and is composed of an inorganic oxide as described above. Even if the gas barrier coating layer described below is further laminated on the vapor deposition layer, a printing layer, an intervening film, a sealant layer, etc., which will be described later, may be provided.

The gas barrier coating layer 13 is a coating layer having gas barrier properties, for example, using a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or hydrolysates thereof. Formed. More specifically, a coating agent obtained by mixing a water-soluble polymer dissolved in an aqueous (water or water / alcohol mixed) solvent with a metal alkoxide directly or previously hydrolyzed. The coating agent is coated on a vapor-deposited thin film layer made of an inorganic oxide and then dried by heating. Each component contained in the coating agent will be described in more detail.

  Examples of the water-soluble polymer used in the coating agent include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used for the coating agent having the above-described composition, it is preferable because gas barrier properties are most excellent. The PVA here is generally obtained by saponifying polyvinyl acetate. As PVA, for example, complete PVA in which only several percent of acetic acid groups remain from so-called partially saponified PVA in which several tens percent of acetic acid groups remain can be used. I do not care.

The metal alkoxide is a compound represented by a general formula, M (OR) _n (M: metal such as Si, Ti, Al, and Zr, R: alkyl group such as CH ₃ and C ₂ H ₅ ). Specific examples include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] and triisopropoxyaluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], among which tetraethoxysilane and triisopropoxy. Aluminum is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

  It is also possible to add known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, and colorants to the solution as long as the gas barrier properties are not impaired. is there.

  As a method for applying the coating agent, conventionally known methods such as a dipping method, a roll coating method, a screen printing method, a spray method, and a gravure printing method that are usually used can be used.

  The thickness of the gas barrier coating layer 13 is not particularly limited, and the optimum condition varies depending on the type of coating agent constituting it, the coating machine, and its processing conditions. However, when the thickness after drying is 0.01 μm or less, a uniform coating film may not be obtained and sufficient gas barrier properties may not be obtained. On the other hand, when the thickness exceeds 50 μm, cracks are likely to occur in the coating film, which may be a problem. It is preferably in the range of 0.01 to 50 μm, more preferably in the range of 0.1 to 10 μm.

  Further, as described above, a printing layer, an intervening film, a sealant layer, and the like can be laminated on the gas barrier coating layer 13 to provide a packaging material with higher versatility.

  The intervening film is provided in order to increase the bag breaking strength and piercing strength during bag-like packaging materials, and is generally a biaxially stretched nylon film or a biaxially stretched polyethylene terephthalate film in terms of mechanical strength and thermal stability. The biaxially oriented polypropylene film is preferably one kind selected from the group consisting of biaxially oriented polypropylene films. The thickness is determined according to the material and required quality, but is generally in the range of 10 to 30 μm.

  Further, the sealant layer is provided so as to function as an adhesive layer when forming a bag-like package or the like. 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 resin such as a metal cross-linked product. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm.

On the other hand, these printing layers, intervening films, sealant layers, and the like may be provided on the other surface of the film base material on which the vapor deposition layer made of the inorganic oxide is not laminated, as necessary.

  Examples according to the strong adhesion vapor deposition film of the present invention and its production method will be specifically described below. The present invention is not limited to these examples.

On one surface of a 12 μm thick polyethylene terephthalate (PET) film, aluminum oxide was deposited to a thickness of 15 nm by reactive vapor deposition using an electron beam heating method, and a vapor deposition layer was provided. Subsequently, a treatment by ion bombardment using magnetron discharge was performed on the vapor deposition layer of this laminated film provided with the vapor deposition layer under the following conditions using a treatment apparatus as shown in FIG. A strong adhesion vapor deposition film of the invention was prepared.
[Processing conditions]
Processing gas: Air Processing unit pressure: 10Pa
Processing time: 10 sec
Discharge voltage: 400V (DC power supply)

  A strongly adhered vapor deposition film of the present invention according to Example 2 was prepared in the same manner as in Example 1 except that the processing gas was nitrogen, the processing unit pressure was 15 Pa, and the discharge voltage was 350 V.

  The processing by plasma ion shower was performed using the processing apparatus as shown in FIG. 4 on the same conditions as Example 1, and the strong contact | adherence vapor deposition film which concerns on Example 3 was created.

  A strong adhesion vapor deposition film of the present invention according to Example 4 was prepared in the same manner as in Example 3 except that the processing gas was changed to nitrogen.

  A vapor deposition film for comparison according to Example 5 was prepared in the same manner as in Example 1 except that the processing unit pressure was 6 Pa and the discharge voltage was 450 V.

  A vapor deposition film for comparison according to Example 6 was prepared in the same manner as in Example 3 except that the processing unit pressure was 6 Pa and the discharge voltage was 450 V.

  A vapor deposition film for comparison according to Example 7 was prepared in the same manner as in Example 1 except that the processing unit pressure was 150 Pa and the discharge voltage was 50 V.

  After the aluminum oxide film was formed, a plasma ion etching apparatus was used to perform a post-treatment on the aluminum oxide vapor deposition layer at a discharge voltage of 2 KV (other conditions are the same as in Example 1). The vapor deposition film for such a comparison was created.

The liquid A and the liquid B shown below are mixed on the respective vapor deposition layers of the strong adhesion vapor deposition films according to Examples 1 to 4 and the vapor deposition films according to Examples 5 to 8 in a compounding ratio (wt%) of 6/4. The mixed solution was applied by a gravure coating method and dried by heating to form a gas barrier coating layer having a thickness of 0.4 μm to obtain 8 kinds of vapor deposited films.

Liquid A: A hydrolyzed solution having a solid content of 3 wt% (in terms of SiO ₂ ) obtained by adding 89.6 g of hydrochloric acid (0.1N) to 10.4 g of tetraethoxysilane and stirring for 30 minutes for hydrolysis.

   Liquid B: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight ratio of water: isopropyl alcohol).

Furthermore, a stretched nylon film (15 μm) and an unstretched polypropylene film (70 μm) are laminated in this order on the gas barrier coating layer of the above eight kinds of vapor-deposited films using a two-component curable polyurethane adhesive. And the packaging material for retorts (The strong adhesion vapor deposition film which concerns on Examples 1'-4 'and the vapor deposition film which concerns on Examples 5'-8') was created.
[Evaluation 1]
The laminate strength of the vapor-deposited films according to Example 1 ′ to Example 8 ′ with the stretched nylon film was measured using an Orientec Tensilon universal testing machine RTC-1250 (based on JIS Z1707). However, the measurement was performed while the measurement site was wetted with water. The results are shown in Table 1.
[Evaluation 2]
Eight pouches having four sides as seal portions were produced using the respective vapor deposition films according to Example 1 ′ to Example 8 ′, and the contents were filled with water. Then, 121 degreeC-30 minute retort sterilization was performed, and the state after a retort was observed visually. The results are shown in Table 1.

It is a section composition explanatory view showing an example of the strong adhesion vapor deposition film of the present invention. It is sectional structure explanatory drawing which shows another example of the strong_contact | adherence vapor deposition film of this invention. It is schematic structure explanatory drawing which shows an example of the processing apparatus by the ion bombardment using the magnetron discharge used in the manufacturing method of this invention. It is schematic structure explanatory drawing which shows an example of the processing apparatus by the plasma ion shower using a magnetron discharge used in the manufacturing method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 11 ... Film base material layer 2, 12 ... Deposition layer 4 ... Target electrode 5 ... Target 6 ... DC power supply 7 ... Magnet 8 ... Positive electrode 9 ... Cooling drum 13 ... Gas barrier coating layer

Claims (10)

  A method for producing a vapor-deposited film comprising at least one vapor-deposited layer made of an inorganic oxide on at least one surface of a film substrate made of a plastic material, wherein after the vapor-deposited layer is formed, a plasma post-treatment using a magnetron discharge on the surface Is applied at a processing unit pressure of 8 to 100 Pa.   The method for producing a strongly adhered vapor-deposited film according to claim 1, wherein the plasma post-treatment is treatment by ion bombardment using magnetron discharge or treatment by plasma ion shower.   The film base material has at least one of polyethylene, polypropylene, polyamides, polyesters, polycarbonate, polyacrylonitrile, polystyrene, polyvinyl chloride, cellulose, triacetyl cellulose, polyvinyl alcohol, polyurethane as a component, or a co-polymer. 3. The method for producing a strongly adhered vapor-deposited film according to claim 1 or 2, comprising any one of a plastic material having a polymerization component or a chemical modification thereof as a component.   The method for producing a strong adhesion vapor-deposited film according to claim 3, wherein the polyester is any one of polyethylene terephthalate, polyethylene naphthalate, boribylene terephthalate, boribylene naphthalate, and a mixture or copolymer thereof. .   The method for producing a strongly adhered vapor-deposited film according to any one of claims 1 to 4, wherein the vapor-deposited layer is made of any of aluminum oxide, silicon oxide, magnesium oxide, or a mixture thereof.   The method for producing a strong adhesion vapor deposition film according to any one of claims 1 to 5, wherein the formation of the vapor deposition layer and the plasma post-treatment are performed in-line.   A gas barrier coating layer formed by applying a water-soluble or water / alcohol mixed solution containing a water-soluble polymer and one or more kinds of metal alkoxides or their hydrolysates onto a vapor-deposited layer subjected to plasma post-treatment, and drying by heating. The method for producing a strongly adhered vapor-deposited film according to claim 1, wherein:   The method for producing a strong adhesion vapor-deposited film according to claim 7, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.   The method for producing a strong adhesion vapor-deposited film according to claim 7, wherein the water-soluble polymer has at least one of polyvinyl alcohol or poly (vinyl alcohol-co-ethylene), cellulose, and starch as a component.   A strong adhesion vapor-deposited film produced by the method for producing a strong adhesion vapor-deposited film according to claim 1.

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