JP6442839B2 - Moist heat resistant gas barrier film and method for producing the same - Google Patents

Description

  The present invention relates to a moisture and heat resistant gas barrier film and a method for producing the same. More specifically, the laminated film for packaging using the same retains excellent gas barrier performance even after a strong retort treatment, and can suppress deterioration and deterioration of contents such as food, and its production. Regarding the method.

  A gas barrier film in which a metal such as aluminum, aluminum oxide or silicon oxide or a metal oxide thin film is formed on a base film of a biaxially stretched polyethylene terephthalate film by a forming means such as a vacuum deposition method is used as a packaging material. The food packaging material in which the gas barrier film is laminated is suitably used as a packaging material having excellent gas barrier properties, water resistance, moisture resistance, boil / retort resistance, and environmental compatibility. Among them, those formed with a metal oxide thin film are widely used because the contents can be visually recognized due to transparency and convenience due to suitability for a microwave oven.

  As the base film constituting these gas barrier films, the polyester film represented by the above-mentioned biaxially stretched polyethylene terephthalate film is suitable because it has excellent heat resistance, dimensional stability, thickness uniformity, etc. It is used for. In particular, in order to be able to be suitably used as a packaging material excellent also in suitability for boil and retort, between a polyethylene terephthalate film as a base film and a deposited thin film layer made of a metal oxide such as aluminum oxide or silicon oxide. Increasing the adhesion strength and preventing the occurrence of delamination and the deterioration of gas barrier performance are effective means for improving the performance.

  For that purpose, glow discharge treatment, plasma treatment, corona treatment, microwave treatment, etc. are carried out as pretreatment of the polyethylene terephthalate film as the base film, or it is made of polyester, acrylic, urethane resin, etc. having good adhesiveness to inorganic substances. An underlayer has been formed by coating (Patent Document 1).

By the way, due to a high demand for food safety, heat sterilization treatment under stronger retort treatment conditions has been performed. Even by heat sterilization treatment with temperatures above 135 ° C. In a recent (high retort treatment), the adhesion strength and the gas barrier performance does not deteriorate, 1 g ^/ (m 2 day) or less of water vapor permeability, 0.5 cc ^/ (m 2 day・ Atm) A film capable of maintaining the oxygen permeability below is required, and the conventional adhesion improving treatment is insufficient.

  Patent Document 2 discloses a method of imparting a functional group to a film surface using reactive ion etching using plasma, but gas barrier performance after retorting at 135 ° C. has not been achieved. Moreover, in practical evaluation of packaging materials for retort use, a peel strength at a low speed of 50 mm / min is required in a wet state, but a sufficient value could not be obtained by the conventional method.

  By the way, a so-called plasma treatment has been generally used as a surface treatment technique for a film base material, but a method of irradiating ions with higher energy than the plasma treatment has attracted attention. Although there is a disclosure regarding a linear ion source that can be dealt with, specific application has been a problem. Patent Document 3 discloses a transparent conductive gas barrier film in which an ion-implanted layer is formed on a plastic film, and a gas barrier layer and a transparent conductive layer are formed thereon. The object is to provide a gas barrier film excellent in moisture and heat resistance. It was not something to do.

JP 2007-210208 A JP 2007-196550 A JP 2008-270115 A

Tokuyasu Sasaki et al. “Development of Linear Ion Source” ULVAC TECHNICAL JOURNAL, No. 63 2005, p. 26

  The present invention is intended to solve such problems of the prior art, and a moisture and heat resistant gas barrier film capable of maintaining the adhesion strength and gas barrier performance of a metal oxide film even after a high humidity and heat state due to strong retort processing conditions. It is an issue to provide.

The present inventors, the modified layer provided Ri by the irradiation of the fast ion by at least a linear-type anode layer type ion source capable of irradiating the fast ion in the surface layer of the one surface of the polyester film is provided, on its A metal oxide layer and a protective layer are sequentially provided, and the above problem can be solved by assuming that the low-speed wet adhesion strength between the modified layer and the metal oxide layer after retorting at 135 ° C. for 30 minutes is 1 N / 15 mm or more. I found it.

Further, as a method for producing this moisture and heat resistant gas barrier film, in a vacuum vapor deposition apparatus for continuously forming a metal oxide layer on a polyester film in a vacuum chamber, between the unwinding portion of the film and the metal oxide layer vapor deposition portion. The film surface layer is changed by a linear anode layer type ion source that can irradiate high-speed ions simultaneously to the entire width in the width direction of the film. Thus, a method for producing a moisture and heat resistant gas barrier film has been developed, in which a metal oxide layer is subsequently formed , and a protective layer is further formed thereon.

  The laminated film for packaging using the moisture and heat resistant gas barrier film of the present invention is a highly reliable packaging material that can be stored for a long period of time with little deterioration in adhesion strength and gas barrier performance even by high retort processing. Can do.

It is a structure of the moisture-heat resistant gas barrier film of this invention. It is an example of the manufacturing apparatus used for this invention.

  FIG. 1 shows the structure of the moisture and heat resistant gas barrier film of the present invention. A reforming layer 2 is formed on the surface layer of the polyester film 1, and a metal oxide layer 3 and a protective layer 4 are sequentially formed thereon.

FIG. 2 shows an example of a vapor deposition machine of a production apparatus used in the method for producing a moisture and heat resistant gas barrier film of the present invention. The polyester film exits from the unwinding roll 13 and is irradiated with high-speed ions in front of a linear anode layer type ion source 17 that generates high-speed ions. The polyester film is wound around the cooling drum 15 and passes over the evaporation source. In doing so, a metal oxide layer is deposited. Then, it is wound up on the winding roll 14. By providing the ion current measurement electrode 18 at a position facing the ion source on the back side of the polyester film 1, the ion current and ion energy distribution can be measured without passing the polyester film in front of the ion source. . The electrode for measuring the ionic current may be provided on the front side of the polyester film. After the measurement, the ion current measuring electrode is removed, or it is retracted by a mechanical mechanism at a position where it does not interfere with the fast ion irradiation to the polyester film. Can be implemented.

  The polyester of the polyester film in the present invention is a general term for polymers having an ester bond with a carboxylic acid and an alcohol, and is typically a condensation polymer of a dicarboxylic acid and a diol, such as polyethylene terephthalate (PET), polyethylene naphthalate. Phthalate (PEN) and the like are manufactured industrially at low cost. Among these, PET is excellent in moldability and physical property balance, and a biaxially stretched film is widely used as a packaging material.

  In conventional plasma treatment, the film surface is exposed to atmospheric pressure corona discharge or low-temperature plasma under reduced pressure to give functional groups only to the surface, and the formed functional groups and the deposited metal or metal oxide In the present invention, the gas barrier after retorting is performed by modifying the surface layer by irradiating high-speed ions on the surface layer of at least one surface of the film. This is intended to stabilize the performance. In fact, it is presumed that when high-speed ions are irradiated, a part of the polymer is decomposed by the energy, and oxygen and hydrogen in the molecular chain are excluded, thereby forming a carbon-rich layer. Under high-temperature high retort treatment conditions such as 135 ° C, the effect of chemical bonding by conventional plasma treatment is attenuated by the movement of the polymer chain, whereas the carbon-rich layer formed by fast ions has excellent heat resistance. Therefore, it is considered that the metal oxide layer hardly moves even at a high temperature, and that the bond with the metal oxide layer is firmly maintained and the adhesion of the metal oxide layer is ensured.

  The protective layer is laminated on the metal oxide layer, and the gas barrier performance is further enhanced by making up for defective portions such as pinholes in the metal oxide layer by its own gas barrier performance. Moreover, it is preferable that it is excellent in heat resistance, and can protect a metal oxide layer under the high temperature by a retort process. Further, at the time of processing, it is possible to mechanically prevent the metal oxide layer from cracking due to excessive bending, stretching, rubbing, and the like and deteriorating the gas barrier performance.

  The protective layer is preferably excellent in gas barrier performance due to such a function, as well as having high transparency, heat resistance, moisture resistance, mechanical strength, and good adhesion to a metal oxide. Examples of the resin excellent in gas barrier performance include a resin having a small free volume in which a bond between polymer chains such as a polymer having a nitrile group represented by polyacrylonitrile and polyvinyl alcohol (PVA) is strong. In consideration of coating properties, heat resistance, and water resistance, these resins can be used as solvent-soluble acrylic resins having a nitrile group or a hydroxyl group, and having the hydroxyl group crosslinked with an isocyanate after coating. An organic-inorganic hybrid film obtained by applying and drying a liquid obtained by condensation polymerization of a PVA-based water-soluble resin and a metal alkoxide can be particularly preferably used. These protective layers are laminated on the metal oxide layer by a conventional method such as gravure roll coating.

  By protecting the metal oxide layer on both the upper and lower sides in this way, it is possible to prevent deterioration of gas barrier performance and adhesion strength after elapse of a high temperature and high humidity state due to high retort treatment.

  Prior to the formation of the metal oxide layer, a modified layer formed by irradiation with fast ions is formed on the surface layer of at least one surface of the polyester film in the present invention. In normal low-pressure plasma treatment (or glow discharge treatment), the surface layer is modified by ion irradiation. In this case, the energy of ions is set to about 0.1 to several eV, and the effect of the surface layer modification. Is limited to the surface layer only.

  In the present invention, the thickness for modifying the surface layer on one side of the polyester film is preferably 10 nm to 200 nm. If it is 10 nm or less, it is difficult to obtain the expected effect. When the thickness exceeds 200 nm, the surface layer is excessively modified and coloring occurs, and the quality as a transparent film is lowered. Moreover, as a result of the loss of the strength of the modified layer, the adhesion strength is weakened. By setting the thickness to 200 nm or less, it is preferable because a transparent modified layer can be obtained with good productivity and without coloring due to excessive treatment.

  In order to obtain the appropriate modified layer thickness, it is important to irradiate high-speed ions of preferably 100 eV or more.

  The energy of the fast ions to be irradiated has a characteristic distribution depending on the mechanism of the ion source. In general ion sources, the mechanism for generating plasma, the mechanism for extracting ions from the plasma, and the mechanism for applying acceleration voltage to the extracted ions are independent, and high-speed ions with a sharp energy distribution according to the acceleration voltage are generated. Can be obtained. On the other hand, in the anode layer type ion source, which will be described later, the above mechanism is not independent, so that the ion energy is distributed.

  The average ion energy weighted and averaged by the energy of ions is preferably in the range of 100 eV to 1 keV. By setting it as 100 eV or more, the efficiency of modification of the surface layer of the polyester film can be increased. Since the average ion energy is about 150 eV, the modified layer is formed more efficiently, and at 300 eV, it is formed sufficiently efficiently. If the average ion energy is made higher than this, an appropriate region is obtained up to about 1 keV. If this is exceeded, the treatment becomes excessive and not only the modified layer is formed, but also the modified layer is etched by high energy, resulting in a waste of productivity. Further, due to the black coloration of the modified layer, there may be restrictions when used as a transparent packaging material.

In the present invention, the degree of modification of the surface layer of the polyester film can be adjusted by the following parameters. The energy of ion means the energy which one ion gives to the polyester film surface layer. The ion current is a current flowing through the irradiated ion particles, and corresponds to the number of ions per time incident for modification. When processing while feeding a film, the product of the width of the film and the feeding speed is the processing area per unit time. The degree of surface modification of the polyester film is determined by dividing the power value, which is the product of the average ion energy Ea and the ion current I, by the treatment area per unit time, and the irradiation energy value per unit area (hereinafter referred to as irradiation energy density). It is expressed as Ea × I / (v × W) as (J / m ² ). Here, the film feed speed is v (m / s), and the film width is W (m).

The 800 J / ^{m 2} range of 20 J / ^{m 2} for irradiation energy density is the preferred region in the present invention. A surface modification effect sufficient by setting it to 20 J / m ² or more can be obtained, and if it is set to 800 J / m ² or less, modification of a colorless and transparent polyester film without brown coloring can be performed without excessive treatment. It can be a quality layer.

  Appropriate irradiation energy conditions as described above can be achieved by adjusting parameters such as the flow rate of gas introduced into the ion source, the operating pressure, and the operating voltage, and appropriately selecting the film feed rate.

  When neutralizing the charge by electron shower during ion irradiation, the electric field formed by the irradiated ions can be prevented from becoming repulsive to the subsequently irradiated ions, enabling efficient irradiation. Become. When a filament is installed in the path of the ion beam and a current is passed, thermoelectrons are emitted and the charge of the ion beam is neutralized. Also, if there is a charged film surface, it is attracted to an electric field and electrons reach to neutralize the charge on the film surface. When the maintenance of filament replacement reduces the efficiency of maintenance of the apparatus, only the electrons may be extracted from the plasma by RF discharge using a mesh-shaped extraction electrode and irradiated onto the film surface.

  The type of ions to be irradiated is not particularly limited, but it may be selected from harmless ion species that are not problematic for food packaging. Those that are gaseous at room temperature are suitable for handling, and in addition to rare gases, nitrogen, oxygen Gas ions such as hydrogen and carbon dioxide are suitable in terms of practicality. Among them, oxygen, nitrogen, and argon ions are advantageous in terms of cost.

  A metal oxide layer made of aluminum oxide is suitable from the viewpoint of performance and productivity, but is not limited thereto, and silicon oxide, zinc oxide, magnesium oxide, titanium oxide, or the like may be used. In addition, other oxides such as silicon oxide may be mixed into the aluminum oxide by multi-source deposition in order to improve chemical stability or optimize barrier properties. In addition, the metal oxide layer is effective as long as it is a transparent inorganic layer, and may be a nitride.

  The shape of the ion source used for fast ion irradiation of the present invention can be uniformly irradiated in the width direction of the running polyester film, and is installed in a vapor deposition apparatus for forming a metal oxide layer by vapor deposition. A compact one that can be made is desirable. The shape of an ion beam by a general ion source is circular, and in order to obtain a uniform ion beam in the film width direction, a plurality of ion sources can be used in the width direction. There is a problem in the influence of the interference and the uniformity in the width direction of the ion beam. On the other hand, an ion source called a linear type meaning that it is elongated is preferably used because it can perform uniform processing in the film width direction by arranging the longitudinal direction of one ion source in the film width direction. it can.

  A typical linear type is the anode layer type described in Non-Patent Document 1. That is, a magnetic field is formed in the gap width direction of the racetrack gap, and a positive voltage is applied to the gap (cathode) to the anode disposed on the back of the opening, and electron hole motion based on the gap magnetic field This is an ion source that enhances plasma and accelerates ions. A linear shape can be obtained by extending the shape of the race track, which is an ion generating portion, in the width direction of the film, and uniform high-speed ion irradiation can be performed in the width direction of the film.

  The degree of vacuum inside the ion source for fast ion irradiation must be above a certain pressure in order to maintain the plasma and take out large current ions, while the extracted fast ions are irradiated before the polyester film is irradiated. The pressure outside the ion source is preferably set low so as not to lose energy due to collision with the residual gas, and is preferably set to a pressure of 0.1 Pa or less.

In the present invention, a vacuum deposition apparatus for continuously forming a metal oxide layer on a polyester film in a vacuum chamber is used, and the film is installed between the unwinding part of the film and the metal oxide layer deposition part. The film surface layer is modified by a linear anode layer type ion source capable of simultaneously irradiating high-speed ions to the entire width in the width direction of the film, and subsequently a metal oxide layer is formed. shall be the manufacturing methods, for adjusting the operating environment of the ion source, they are also effective to perform the differential exhaust for exhausting the inside it for an exhaust system surrounds the ion source section.

  Since the collision of ions with the residual gas can be reduced as the ion source and the polyester film are closer, it is desirable that the distance between the ion extraction opening of the ion source and the film be close to 15 cm or less.

The moisture and heat resistant gas barrier film of the present invention has a low-speed wet adhesion strength of 1 N / 15 mm or more between the modified layer and the metal oxide layer after retorting at 135 ° C. for 30 minutes . The low-speed wet adhesion strength is the adhesion strength when peeling at a low speed of 60 mm / min or less while supplying water to the peeling portion. By setting the low-speed wet adhesion strength to 1 N / 15 mm or more, the water vapor transmission rate and oxygen transmission rate after the retort treatment can be kept low, which is preferable.

  According to the present invention, a high-quality moist heat resistant gas barrier film can be produced with high productivity.

  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) Total light transmittance The total light transmittance (%) of the barrier film after vacuum deposition was measured with a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. 80% or more was made a suitable range as a transparent packaging material.

(2) Retort treatment Toyo Morton Co., Ltd. dry laminate adhesive AD-503 type 20 parts by weight, Toyo Morton Co., Ltd. hardener CAT-10 type 1 part by weight, and ethyl acetate 20 parts by weight, The mixture was stirred for 30 minutes to prepare a dry laminate adhesive solution having a solid content of 19% by weight. Next, the adhesive solution was applied to the surface of the protective layer of the moisture and heat resistant gas barrier film of the present invention by a bar coating method, and dried at 80 ° C. for 45 seconds to form a 3.5 μm adhesive layer. Non-stretched nylon film Toray Film Processing Co., Ltd. “Rayfan” (registered trademark) NO1401 type (thickness 30 μm) is layered on the adhesive layer surface, and heat roll using Fujimi Co., Ltd. “Lamipacker” (LPA330) Were bonded together by heating to 40 ° C. Next, an unstretched polypropylene film “Treffan” (registered trademark) NO ZK100 type (thickness: 70 μm) was bonded by the same method. This laminate film was aged in an oven heated to 40 ° C. for 2 days to cure the adhesive.

  A cut sample was prepared by cutting the laminate film into a 15 cm square. Two cut samples were overlapped so that the unstretched polypropylene film faces each other, and a heat sealer was used to heat-seal the edge 10 mm of each of the three sides to prepare a 150 mm square package.

  Next, the package was retorted at a temperature of 135 ° C. for 30 minutes using an autoclave (SR-24 type) manufactured by Tommy Seiko Co., Ltd.

(3) Low-speed wet adhesion strength after retort treatment After retort treatment, the package is cut into a width of 15 mm and a length of 150 mm to create a cut sample. Using “Tensilon” (PTM50 type) manufactured by Orientec Co., Ltd. While the moisture-heat resistant gas barrier film and the nylon film were used as an interface, water was applied to the interface with a cotton swab, and the strength was measured by peeling at a pulling rate of 50 mm / min by a 180 ° peel method. These measurements were performed using two different cut samples, and the average value obtained was defined as the low-speed wet adhesion strength (N / 15 mm) after retorting. 1N / 15 mm or more was regarded as acceptable.

(4) Oxygen permeability after retort treatment After retort treatment, a sample was prepared by cutting the package into a width of 100 × 100 mm, and the oxygen permeability (cc / (m ² day · atm)) was measured according to JISK7126-2 (established 2006) According to August 20, the measurement was performed under the conditions of 23 ° C. and 0% RH using an oxygen permeability measuring device OX-TRAN 2/20 manufactured by Modern Control. The average value of 3 samples was obtained. The oxygen permeability of 0.5 cc / (m ² day · atm) or less was set within the acceptable range.

(5) Water vapor permeability after retort treatment After retort treatment, a sample is prepared by cutting the package into a width of 100 x 100 mm, and the water vapor permeability (g / m ² day) is set to JISK7129B (established on March 20, 2008). Accordingly, measurement was performed under the conditions of 40 ° C. and 90% RH using a water vapor permeability measuring device Permatran-W3 / 30 manufactured by Modern Control. The average value of 3 samples was obtained. The water vapor transmission rate was 1 g / m ² day or less within the acceptable range.

(6) Measurement of the thickness of the modified layer The thickness of the modified layer was determined by the following method. After performing the ion beam treatment of polyester, it was taken out into the atmosphere and analyzed by TOF-SIMS analysis (TOF-SIMS5 by IONTOF).

Secondary ions obtained by etching with a primary ion source (Ar cluster ion beam, 2.5 keV, 0.35 nA) and irradiation with bismuth liquid metal (Bi ₃ ⁺ , 10 keV, 0.5 pA) at each depth The molecular fragment (fragment) which is is counted. The corresponding molecular formula was identified from the mass of the fragment, and the data was aggregated as a change with respect to the etching time. The etching depth with respect to the etching time corresponds to 1 nm in terms of SiO ₂ , but it was converted to the etching depth by multiplying this by 5 times the etching rate ratio of polyethylene terephthalate to SiO ₂ which is separately known.

To determine the thickness of the modified layer, the ratio of the peak areas of C ₆ H ₁₆ N ⁺ and C ₇ H ₇ ⁺ was used. C ₆ H ₁₆ N ⁺ is caused by a component in which part of molecular bonds of the polyester is broken by ion bombardment and nitrogen in the atmosphere is taken into the polyester. C ₇ H ₇ ⁺ corresponds to a component that is not changed by the ion beam treatment and is evenly distributed from the surface layer. This may be due to the benzene ring having a strong atomic bond. Taking advantage of the fact that C ₆ H ₁₆ N ⁺ is detected as the ion beam treatment is stronger, the ratio to C ₇ H ₇ ⁺ is used as an index of the modified layer. In this ratio, the depth of the modified layer was defined by defining a region of 0.1 or more as a modified layer.

Example 1
A. Formation of modified layer and metal oxide layer on polyester film Between the film unwinding part and the vapor deposition part of a continuous winding type vapor deposition machine (manufactured by ULVAC, Inc.), an ion of linear type anode layer type with an effective length of 1 m. A source (Veeco, ALS1000L) was installed at a distance of 50 mm from the film running surface. As the power source for the ion source, the SH type of Grassman High Voltage Company was used. An electrode for measuring the ionic current that has been subjected to water cooling of 1 m × 200 mm is provided at a position 10 mm away from the film running surface to the back side of the film, and the ionic current is changed while the positive retarding voltage is changed while the ion source is operated. It was measured. From the relationship between the retarding voltage and the ion current, the average energy Ea (eV) of the ions was calculated from the ion energy distribution in the same manner as in Non-Patent Document 1. In addition, the ionic current I (A) in a state where no retarding voltage was applied was also measured. First, oxygen was introduced into the ion source at 80 cc / min, and the ion source was operated at an anode voltage of 2 kV and an anode current of 860 mA. At this time, it was confirmed that the average energy Ea of ions was 0.6 keV and the ion current was 650 mA. Similarly in Example 2 and later, the average energy and ion current of ions under the operating conditions of the ion source were measured in advance.

A biaxially stretched polyethylene terephthalate film for packaging ("Lumirror" (registered trademark) P60 manufactured by Toray Industries, Inc., thickness 12 μm, width 1000 mm) is set as a polyester film in the film unwinding portion, and an ultimate pressure of 3 × A vacuum was drawn to 10 ⁻³ Pa. Next, the crucible containing granular aluminum (manufactured by Vacuum Metallurgical Co., Ltd., purity 99.99%) is heated at high frequency, and the film is run at a speed of 4 m / s. The amount of evaporation was set by adjusting the input power so as to be 10%. The ion source was operated under the above conditions to irradiate oxygen ions, and oxygen was introduced into the vapor deposition portion to form an aluminum oxide layer. The temperature of the film cooling drum at this time was −30 ° C. Thereby, an aluminum oxide layer having a thickness of 10 nm was formed. The irradiation energy density at this time was 0.6 keV × 650 mA / (4 m / s × 1 m) = 98 J / m ² . The degree of vacuum was 2 × 10 ⁻² Pa with a BA gauge pressure gauge attached to the wall of the vacuum chamber beside the ion source.

B. Preparation of Protective Layer Coating Liquid The resin applied as the protective layer is an acrylic copolymer, and each monomer of acrylonitrile (AN), 2-hydroxyethyl methacrylate (2-HEMA) and methyl methacrylate (MMA) is 20:50. : Copolymerized at a ratio (mass%) of 30 was prepared. The copolymer resin is dissolved in a mixed solvent of methyl ethyl ketone (MEK), pyromellitic dianhydride (PMDA), propylene glycol monomethyl ether (PGM) propyl acetate, propylene glycol monomethyl ether (PGM) and n-propyl alcohol to obtain a solid. A solution of a copolymer resin having a partial concentration of 6.93% by mass was obtained.

  3-Aminopropyltriethoxysilane was mixed with a mixed solvent of acetone and water, stirred for 2 hours and hydrolyzed to obtain a solution having a solid content ratio of 14.8%. This was mixed with a curing agent HX-75 (solid content concentration: 75% by mass) based on xylene diisocyanate manufactured by DIC Corporation and methyl ethyl ketone to obtain a solution having a solid content of 11.8%. 103.8 parts by weight of this solution and 144.5 parts by weight of the above acrylic copolymer resin solution were mixed to prepare a coating solution for a protective layer having a solid content of 9.0%.

C. Formation of Protective Layer On the aluminum oxide layer of the film, the protective layer coating solution is used in a roll-to-roll direct gravure coating machine, using a gravure roll with a lattice pattern of 59 lines / cm and a depth of 64 μm, After coating on the aluminum oxide layer at a speed of 100 m / min, it was dried in a drying furnace to form a protective layer having a thickness of 0.2 μm, and a moisture and heat resistant gas barrier film was prepared. Drying conditions were set so that the film temperature at the time of drying was 140 ° C. using a heat label. Various properties of the film after retorting were measured and listed in Table 1.

(Example 2)
In the same manner as in Example 1, the anode voltage of the ion source was 3 kV, the anode current was 1680 mA, and the feed rate was 8 m / s. The average energy Ea of ions was 0.9 keV, and the ion current was 1430 mA. The irradiation energy density per unit area was 161 J / m ² and the characteristics were good.

Example 3
In the same manner as in Example 1, the anode voltage of the ion source was 1 kV, the anode current was 390 mA, and the feed rate was 3 m / s. The average energy of ions was 0.3 keV, the ion current was 260 mA, the irradiation density per unit area was 26 J / m ² , and the characteristics were good.

(Example 4)
In the same manner as in Example 1, the anode voltage of the ion source was 0.6 kV, the anode current was 210 mA, and the feed rate was 3 m / s. The average energy of ions was 0.2 keV, the ion current was 150 mA, and the irradiation energy density was 10 J / m ² . The water-resistant adhesion was 1 N / 15 mm, the oxygen permeability was 0.5 cc / (m ² day · atm), and the water vapor permeability was 1 g / (m ² day).

(Example 5)
In the same manner as in Example 1, the ion source voltage was 3 kV, the ion current was 1680 mA, and the feed rate was 1.5 m / s. The irradiation energy density was 858 J / m ² . The retort resistance was excellent. However, since the high-speed ion irradiation was too strong, the total light transmittance was 79%, which was slightly lower, and there was a concern that the use was somewhat limited.

(Example 6)
In Example 1, the protective layer was produced as follows. Compared to Example 1, good results were obtained.

A. Preparation of Protective Layer Coating Liquid Solution 1 is a hydrolyzed liquid composed of ethyl silicate 40 (manufactured by Tama Chemical Co., Ltd.), isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water. Solution 2 is a mixed liquid composed of an aqueous polyvinyl alcohol solution, a silane coupling agent (epoxysilane SH6040, γ-glycidoxypropyltrimethoxysilane manufactured by Toray Dow Corning Co., Ltd.), acetic acid, isopropyl alcohol and ion-exchanged water. EVOH (ethylene copolymerization ratio 29%) is dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water to obtain a solution 3.

Solution 2 was added to solution 3 and stirred. Next, Solution 2 was added and stirred to obtain a colorless and transparent gas barrier composition.
Solution 1 Ethylsilicate 40 11.460 (wt%)
Isopropyl alcohol 17.662
Aluminum acetylacetone 0.020
H ₂ O 13.752
Solution 2 Polyvinyl alcohol 1.520
Silane coupling agent 0.050
Isopropyl alcohol 13.844
H ₂ O 35.462
Acetic acid 0.130
Solution 3 EVOH 0.610
Isopropyl alcohol 3.294
H ₂ O 2.196
B. Formation of Protective Layer On the aluminum oxide layer of the film, the gas barrier composition was used in a roll-to-roll direct gravure coating machine, using a gravure roll with a lattice pattern of 18 lines / cm and a depth of 200 μm, and the speed After coating on the aluminum oxide layer at 100 m / min, drying was performed in a drying furnace to form a protective layer having a thickness of 0.25 μm, and a moisture and heat resistant gas barrier film was prepared. Drying conditions were set so that the film temperature during drying was 100 ° C. using a heat label.

(Comparative Example 1)
In Example 1, a protective layer was formed and prepared in the same manner as in Example 1 except that the aluminum oxide layer was deposited without performing ion irradiation.

(Comparative Example 2)
In Example 1, a magnetron cathode with copper as a target was subjected to a surface treatment in place of an ion beam by passing a film through plasma generated by discharging at a high frequency in 1 Pa of oxygen. The shape of the cathode was 1.3 m × 100 mm, and the voltage and current during discharge were 320 V and 9.2 A. Otherwise, an aluminum oxide layer was deposited in the same manner as in Example 1 to form a protective layer.

(Comparative Example 3)
In Example 1, it produced similarly to Example 1 except not forming a protective layer.

DESCRIPTION OF SYMBOLS 1 Polyester film 2 Modified layer 3 Metal oxide layer 4 Protective layer 11 Vacuum tank 12 Vacuum pump 13 Unwinding roll 14 Winding roll 15 Cooling drum 16 Evaporating source 17 Ion source 18 Ion current measuring electrode 19 Power source for operating the ion source

Claims (5)

At least one surface of the surface layer to the reforming layer provided Ri by the irradiation of the fast ion by the linear-type anode layer type ion source capable of irradiating a high-speed ion is provided, the metal oxide layer thereon of a polyester film, A moisture and heat resistant gas barrier film in which protective layers are provided in this order, and the low-speed wet adhesion strength between the modified layer and the metal oxide layer after retorting at 135 ° C. for 30 minutes is 1 N / 15 mm or more. The wet heat resistant gas barrier film according to claim 1, wherein the metal oxide layer is made of aluminum oxide. The moisture and heat resistant gas barrier film according to claim 1 or 2, wherein the modified layer has a thickness of 10 nm to 200 nm. In a vacuum vapor deposition apparatus for continuously forming a metal oxide layer on a polyester film in a vacuum chamber, it is installed between the unwinding part of the film and the metal oxide layer vapor deposition part, and along the width direction of the film It consists of a cathode having a racetrack-shaped gap extending in a straight portion and an anode behind the gap, and a magnetic field line extends in the width direction of the gap. By applying a positive voltage to the anode with respect to the cathode, the anode The composition of the surface layer of at least one side of the film is changed by a linear anode layer type ion source that can generate plasma in the front space and simultaneously irradiate high-speed ions to the entire width of the film through the gap. And then forming a metal oxide layer, and further forming a protective layer thereon. Method of manufacturing the A film. The average energy Ea of fast ions irradiated to the polyester film from the linear anode layer type ion source is in the range of 100 eV to 2 keV, the ion current I (A) due to the fast ions, the feed speed v (m / m) of the polyester film. 5) The irradiation energy density (J / m ² ) determined by the formula of Ea × I / (v × W) from the width W (m) of the film is in the range of ²⁰ to 800 J / m ^2. The manufacturing method of the heat-and-moisture resistant gas barrier film of description.

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