JP2003285387A - Gas-barrier film roll, laminate and packaging bag using the roll - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier film roll which is excellent in uniformity of transparency and gas-barrier properties, printing processability, lamination processability, and bag-making processability and useful for filling and packaging food and drink, a medicine, cosmetics, electronic parts, etc., a laminate and a packaging bag using the roll. <P>SOLUTION: In the gas-barrier film roll, a thin gas-barrier film of an inorganic oxide is vapor-deposited on at least one surface of a base material roll film. The gas barrier film roll is taken out of a vacuum deposition apparatus and, after it is rewound in an environment of which the absolute humidity is 0.008-0.018 kg/kg so that the vapor deposition surface is in contact with air at least once in the environment, it is preserved in a constant temperature environment of 30-60°C in a roll state for at least a constant period to uniformly enhance the transparency and gas-barrier properties of the film roll over the whole in the length and width directions of the roll. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a film roll having excellent transparency, gas barrier properties, moisture resistance, printability and flexibility. Furthermore, the present invention relates to a laminate in which a heat-sealable resin layer is laminated via a printing layer, an adhesive layer, an anchor coat layer, and the like, and a packaging bag using the same.

[0002]

2. Description of the Related Art Heretofore, as a film excellent in gas barrier property, a film formed by vapor-depositing metal aluminum on a plastic film or a film formed by coating vinylidene chloride or ethylene vinyl alcohol copolymer is known. In addition, in recent years, it has become known that inorganic oxide thin films such as silicon oxide and aluminum oxide are laminated by a vacuum vapor deposition method or a CVD (chemical vapor deposition) method.

A gas barrier film obtained by laminating an inorganic oxide thin film on a substrate film by a vacuum vapor deposition method or the like may not exhibit the gas barrier property as expected immediately after vapor deposition.
In addition, the transparency may be blackish brown or dark brown immediately after vapor deposition due to the coloring of the deposited film. It is considered that this is because the inorganic oxide thin film immediately after vapor deposition is in an incompletely oxidized state, and unbonded sites remain so that the film density is rough. Generally, colored ones are shunned as transparent packaging materials, but especially yellowish ones are shunned because the contents look old.

As a method for solving these problems, the following proposals have been made. For a reactive vapor deposition gas barrier film of aluminum oxide, a transparent gas barrier film with improved transparency and gas barrier properties is obtained by vapor-depositing moisture off-line after vapor deposition and further performing heat treatment at a temperature above the moisture adsorption temperature. A method of manufacturing has been proposed. (Patent No. 2638
Further, there is proposed a method for producing a laminated packaging material in which the vapor deposition surface of a plastic film vapor-deposited with silicon oxide is coated with an aqueous liquid and heated and dried to improve transparency and gas barrier properties. (JP-A-6-5616
In addition, the vapor deposition surface of a plastic film vapor-deposited with silicon oxide is coated with an aqueous hydrogen peroxide solution, and the mixture is left in a dark place or a place with a predetermined brightness at a predetermined temperature for a predetermined time to obtain transparency and a gas barrier. A silicon oxide vapor deposition film having improved properties and a method for producing the same have been proposed. (See Japanese Patent Application Laid-Open No. 8-197675) In addition, a manufacturing method has been proposed in which a reactive vapor deposition gas barrier film of aluminum oxide is allowed to stand for one week or more in an environment of 25 ° C. and relative humidity of 50% RH. (See JP-A-2000-355070) Furthermore, during vapor deposition, the aluminum oxide vapor deposition film was wound up so that the vapor deposition surface was on the inside, and then rewound so that the vapor deposition surface was on the outside. ~ 100
A manufacturing method has been proposed in which it is left in an environment of% RH for 48 hours or more. (See Japanese Patent Application Laid-Open No. 11-262969) In any case, a gas barrier thin film made of an inorganic oxide having a thin film structure including an unbonded portion in an incompletely oxidized state is increased in oxidation degree by various means or the thin film structure is densified.
This is considered to be the purpose of improving transparency and gas barrier properties.

[0005]

However, in the proposal of Ya, it is necessary to pass through a gravure coater to coat various aqueous solutions, or to pass a water bath, which is disadvantageous in terms of cost and gas barrier property. , In particular, if an aqueous solution is applied to the vapor deposition film while the moisture proof property (water vapor barrier property) is not sufficient, moisture will pass through the vapor deposition film,
The base material absorbs water and causes swelling due to swelling of the base material film, and especially in the case of a base material film made of a water-absorbent resin such as polyamide resin, the dimensional change in moisture absorption is large, and the gas barrier of inorganic oxides The film is cracked, which causes deterioration of the gas barrier property. Furthermore, applying heat to dry the coated aqueous solution also causes damage to the gas barrier film due to heat shrinkage of the base film,
There is a concern that the gas barrier property will deteriorate.

[0006] Further, in the proposal, there is mentioned a method of allowing it to stand under a specific temperature and humidity or high temperature and high humidity to adsorb the water necessary for reforming. However, due to its own gas barrier property, it is difficult to uniformly adsorb moisture or oxygen essential for reforming to the inside of the roll, and as a result, properties such as transparency and gas barrier property are taken in the length direction of the roll,
There is a concern that the film may vary in the width direction.

[0007]

As a result of various investigations to solve the above problems, the present inventors have found that an inorganic oxide is formed on at least one side of a base roll film by a winding vacuum deposition method. The gas barrier film roll on which the gas barrier thin film consisting of was vapor-deposited was taken out from the vacuum vapor deposition apparatus, and was rewound in an environment where the absolute humidity was 0.008 to 0.018 kg / kg, with the vapor deposition surface being in contact with air under the environment at least once. After that, the invention led to the invention that an excellent gas barrier film roll having improved transparency and gas barrier properties can be obtained by storing it in a constant temperature environment of 30 to 60 ° C. for a certain period or longer.

That is, the present invention is a gas barrier film roll obtained by vapor-depositing a gas barrier thin film layer made of an inorganic oxide on at least one side of a substrate film by a winding-type vacuum vapor deposition method. The gas barrier film roll is taken out from a vacuum vapor deposition apparatus. In an environment where the absolute humidity is 0.008 to 0.018 kg / kg, the vapor deposition surface is rewound at least once in contact with the air in the environment, and then rolled and stored in a constant temperature environment of 30 to 60 ° C for a certain period or longer. The gas barrier film roll is characterized in that the color difference b value in a state where four films cut out from the roll after storage are stacked is within ± 3.0 in the width direction and the length direction of the roll. Further, the gas barrier film roll is characterized in that the gas barrier thin film layer made of an inorganic oxide of the gas barrier film roll is a composite oxide containing at least an aluminum metal oxide and a silicon oxide, and the base film has two layers. A gas barrier film roll characterized by being an axially stretched polyamide film or a biaxially stretched polyester film, further comprising a vapor deposition anchor layer between the substrate film and the gas barrier thin film layer. It is a roll. Further, the present invention is characterized in that, in the above gas barrier film loam, a printing layer is provided on the gas barrier thin film layer if necessary, and then a heat sealable resin layer is laminated via an anchor coat agent layer or an adhesive layer. And a heat-sealable resin layer which is heat-sealed to form a bag.

The base film referred to in the present invention is a film obtained by melt-extruding an organic polymer and, if necessary, stretching, cooling and heat-setting in the longitudinal direction and / or the width direction, or by a solution casting method. For example, the film is wound up. As the organic polymer, polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, Polyamideimide, polyimide, polyetherimide, polysulfone, polyphenylene sulfide,
Examples thereof include polyphenylene oxide, polycarbonate and polyarylate. These (organic polymer) organic polymers may be copolymerized or blended with other organic polymers. A biaxially stretched polyamide film or a biaxially stretched polyester film is particularly preferably used from the viewpoint of a balance between suitability for vapor deposition as a vapor deposition base film and suitability as a packaging bag made of a gas barrier film.

Further, known additives such as an ultraviolet absorber, an antistatic agent, a plasticizer, a lubricant and a coloring agent may be added to the organic polymer, and its transparency is not particularly limited. However, when used as a transparent gas barrier film, those having a transmittance of 50% or more are preferable. The substrate film of the present invention, as long as the object of the present invention is not impaired, prior to depositing the inorganic oxide thin film layer, the film is subjected to corona discharge treatment, glow discharge treatment, and other surface roughening treatment. May be given. The base film of the present invention has a thickness of 5 to 50.
The range is preferably 0 μm, more preferably 8 to 100.
It is in the range of μm.

The vapor deposition anchor layer referred to in the present invention is not particularly limited as long as the adhesion between the substrate film and the gas barrier thin film layer is improved and the gas barrier property after various post-processing is maintained. , Polyester resin, oil-modified alkyd resin, urethane alkyd resin, melamine alkyd resin, epoxy cured acrylic resin, epoxy resin (amine, carboxyl group terminated polyester, phenol,
(Curing with isocyanate), isocyanate resin (curing with amine, urea, carboxylic acid), urethane-
Polyester resin, polyurethane resin, phenol resin, polyester resin, polyamide resin, reactive acrylic resin, vinyl chloride resin, etc. can be used. Further, a resin obtained by solubilizing or water-dispersing these may be used. Among the above materials, the adhesiveness and gas barrier property between the base film and the gas barrier thin film layer are maintained after various post-processing, and thus the graft copolymerization of the polyester resin or the unsaturated polyester resin and the acrylic monomer is carried out. Coalescence is preferred.

The method of providing the vapor deposition anchor layer between the base film and the gas barrier thin film layer in the present invention includes:
Both an in-line method of applying the base material film at the time of manufacturing and an off-line method of applying at a step different from the film manufacturing can be used. Further, known coating methods can be used for coating, for example, roll coating method, reverse coating method, roll brush method, spray coating method, air knife coating method, gravure coating method, impregnation method, curtain coating method and the like. Can be used. From the viewpoint of productivity, it is preferable to provide the vapor deposition anchor layer by an in-line method at the time of manufacturing the base film, but specifically, a graft copolymer-containing solution or the like is applied onto the base film after unstretching or uniaxial stretching. After drying, if necessary, uniaxial stretching or biaxial stretching may be further performed, and further heat setting may be performed. When a graft copolymer-containing solution or the like is applied and dried on the substrate film, the drying temperature is preferably 150 ° C or higher, particularly preferably 200 ° C or higher, which improves the adhesion between the adhesive resin layer and the polyamide-based film. . The thickness of the vapor deposition anchor layer is preferably 0.01 to 1 μm,
More preferably, it is 0.02 to 0.5 μm. If the thickness is too thin, the adhesion between the vapor deposition anchor layer and the substrate film may not be sufficient, and if it is too thick, blocking may occur, which is not preferable.

The roll-up type vacuum vapor deposition method referred to in the present invention is
A vacuum deposition machine that has a coating drum with a cooling function in a vacuum chamber equipped with a vacuum exhaust facility, a running system such as a film roll unwinding and winding mechanism, and an evaporation source that heats and evaporates the evaporation material in the crucible. It is a method of continuously laminating a gas barrier thin film layer made of an inorganic oxide in the longitudinal direction of at least one surface of a base film roll, and if necessary, an opening / closing shutter, a plasma pretreatment machine, a static eliminator, a wrinkle removing roll, and a vacuum. A gauge, a gas introduction port, a film thickness monitor, etc. may be provided.

A vapor deposition material such as a metal or a metal oxide, which is a raw material of a gas barrier thin film made of an inorganic oxide, is put into a crucible made of carbon or a refractory metal, and indirectly or directly by resistance heating, induction heating or an electron gun. The film having a gas barrier property is vapor-deposited on the film by passing through the vaporized base material film which has been adhered to the cooled coating drum. Since resistance heating or induction heating heats the crucible, there is concern that the material forming the crucible may be mixed into the vapor deposition film.However, electron gun heating has the advantage that the vapor deposition material is heated directly and the impurities in the thin film are small. is there. In general, the melting point of metal oxides is considerably higher than that of metals, but there is no restriction on the heat resistance of the crucible in heating with an electron gun, so metal oxides are preferably used as vapor deposition materials. From the viewpoint of the vapor deposition rate, it is preferable to heat the material with an electron gun.

The vapor deposition material such as metal or metal oxide, which is a raw material of the gas barrier thin film made of an inorganic oxide in the present invention, includes magnesium, calcium, aluminum, titanium, silicon, germanium, zirconium,
Metals such as zinc, titanium, chromium, indium and tin, and metal oxides thereof, or composites thereof. The term “metal oxide” as used herein also includes an oxide that is not completely oxidized and is slightly depleted of oxygen, for example, an inorganic oxide that is expressed as SiOx (x = 1.0 to 1.9). From the viewpoint of gas barrier properties, silicon oxide or aluminum oxide is preferable,
Further, a composite oxide of silicon oxide and aluminum oxide is particularly preferable from the viewpoint of bending resistance.

The film thickness of the gas barrier thin film made of an inorganic oxide according to the present invention is preferably 5 to 50 nm, more preferably 10 to 10 in terms of the balance of transparency, gas barrier property and bending resistance.
30 nm. When the film thickness is thinner than 5 nm, it is difficult to obtain practical gas barrier properties, and conversely, when the film thickness is 50 nm or more, cracks inside the thin film due to internal stress of the gas barrier thin film and peeling from the base material are likely to occur. The effect of improving the gas barrier property equivalent to the film thickness cannot be obtained, which is rather disadvantageous in terms of bending resistance and manufacturing cost. The above-mentioned film thickness is measured by a quantitative analysis of a metal element of an inorganic oxide forming a thin film by fluorescent X-ray analysis. A fluorescent X-ray monitor was installed on the roll in the pass line of the winding part from the coating drum in the vacuum vapor deposition machine to monitor online during vapor deposition, and based on the result, the output of the electron gun was finely adjusted and The film thickness can be controlled.

The rewinding of the film roll as referred to in the present invention means that the film roll wound under reduced pressure in a vacuum vapor deposition machine is equipped with equipment such as a film slitter, and the gas barrier thin film surface made of an inorganic oxide contains at least oxygen. By exposing it to the air in which water vapor exists and winding it up,
It refers to the operation of allowing an air layer containing oxygen and water vapor to exist between the layers of the vapor-deposited film roll. The volume ratio of air to the whole film roll is 1 to 5
% Is preferable.

At this time, it is preferable that the surface of the gas barrier thin film made of an inorganic oxide is exposed to air for at least 0.1 seconds. Temporarily rewind line running speed 600m /
When the length is min, the film runs 1 m in 0.1 seconds, so the pass line from unwinding to winding must be at least 1 m or more. At this time, the slitting operation for changing the winding width of the film roll or for aligning the roll end faces is performed as necessary and is not always necessary.

The absolute humidity referred to in the present invention is the absolute amount of water vapor contained in 1 kg of air at a certain temperature, and the unit is kg.
It is expressed as (water vapor) / kg (air). Relative humidity indicates what percentage of the amount of water vapor is contained with respect to the water vapor limit amount that can be contained at a certain temperature, which is represented by a so-called “air diagram”. For example, 1 atm (1013 hPa), 23 ℃
, The limit (saturation) water vapor amount is 0.0177 kg / kg, the absolute humidity is 0.0178 kg / kg at a relative humidity of 100% RH, and the absolute humidity is 0.0087 kg / kg at a relative humidity of 50% RH.

An example of the relationship between relative humidity and absolute humidity in a practical temperature range will be given below. 18 ℃ Relative humidity 65% RH = Absolute humidity 0.0083kg / kg 20 ℃ Relative humidity 55% RH = Absolute humidity 0.0080kg / kg 25 ℃ Relative humidity 45% RH = Absolute humidity 0.0089kg / kg 25 ℃ Relative humidity 85% RH = Absolute humidity 0.0170kg / kg 28 ℃ Relative humidity 35% RH = Absolute humidity 0.0082kg / kg 28 ℃ Relative humidity 70% RH = Absolute humidity 0.0169kg / kg 30 ℃ Relative humidity 65% RH = Absolute humidity 0.0174kg / kg 32 ℃ Relative humidity 60% RH = Absolute humidity 0.0180kg / kg

The humidity environment in which the vapor-deposited film roll is rewound is preferably 0.008 kg / kg or more in absolute humidity, and more preferably 0.008 to 0.015 kg / kg from the viewpoint of working environment. When the absolute humidity is 0.008 kg / Kg or less, the amount of water vapor taken in between the film of the film roll and the film layer during rewinding becomes insufficient. That is, in the subsequent storage step under a constant temperature environment of 30 ° C. or more, the gas barrier thin film made of an inorganic oxide becomes dense and the amount of water required for improving the gas barrier property is insufficient. In addition, discharge due to static electricity due to peeling charging during rewinding is less likely to occur as the absolute humidity increases.
However, when the base film is made of a hygroscopic resin such as a polyamide resin, when the absolute humidity is high, specifically, when the absolute humidity is about 0.02 kg / kg or more, wrinkles due to hygroscopic expansion, it becomes difficult to slip. Roll wrinkles are likely to occur, which may cause damage to the gas barrier thin film layer.

Since the vapor-deposited film roll of the present invention is a gas barrier film itself, the state of the film roll wound under reduced pressure in a vacuum vapor deposition machine or the state of the film roll wound after rewinding operation. However, the amount of oxygen and water vapor that can penetrate into the inside from the outside is extremely small, and improvement of the gas barrier property cannot be expected so much without the rewinding operation in the air having an absolute humidity of 0.008 kg / kg or more as in the present invention.

The constant temperature environment of 30 to 60 ° C. in the present invention means, for example, in a constant temperature tank or a storage room having a temperature adjusting facility, and can be controlled at least within ± 5 ° C. with respect to the set temperature. All you need is the ability. If the average temperature during the storage period is less than 30 ° C, the densification of the gas barrier thin film made of inorganic oxide hardly progresses, and conversely, at 60 ° C or higher, the bleeding of the additive of the base film and the base film itself. Due to the softening, various physical properties are deteriorated and the films are blocked. Regarding humidity, it is preferable to have a humidity control capability in a thermostatic chamber or a storage room that has temperature control equipment, but it is not necessarily required, but it is a structure that does not cause dew condensation, about 30 to 70% RH
It is more preferable if it is maintained at a certain level.

The fixed period of storage in the above-mentioned constant temperature environment is preferably 7 days or longer, more preferably 1 day.
4 days or more. If it is less than 7 days, the densification of the gas barrier thin film made of an inorganic oxide does not proceed so much, and conversely, even if it is stored for a long time, the pace of improvement of the gas barrier property and the transparency gradually decreases. In practice, the storage temperature and storage period are determined by the balance between the required characteristics and inventory management costs. In addition, it has been found that there is a trade-off relationship between storage temperature and storage period to some extent, and within the range that does not impair other physical properties, the storage temperature can be raised as necessary to obtain the target gas barrier properties and transparency. It is possible to shorten the period until it is given. On the contrary, if there is a concern that other physical properties will be affected by raising the temperature, the storage temperature may be set to about 30 ° C. and the period may be extended until the target gas barrier properties and transparency are obtained.

The heat-sealable resin layer referred to in the present invention is
It is a heat-fusible resin layer such as polyethylene or polypropylene, and as a lamination method thereof, a film formed in advance is laminated by a dry lamination method or the like, or is extruded in a molten state by a lamination method or the like. You may make it laminate. Further, various printing may be performed on the vapor deposition surface prior to the lamination with the heat-sealable resin layer. As the printing method, various known printing methods such as gravure printing, flexographic printing and offset printing can be used without departing from the object of the present invention. At this time, for the purpose of improving the wettability of the ink and protecting the vapor deposition surface, a medium coat or a primer coat may be applied as the first color of the print layer.

The packaging bag referred to in the present invention is a laminate obtained by laminating the above heat-sealable heat-sealing resin layer, and heat-sealing the heat-sealing surfaces thereof by a well-known bag-making machine to form a bag. The contents are filled and used at the same time as or after bag making. In the packaging of foods and drinks, pharmaceuticals, cosmetics, electronic devices, etc., a stable gas barrier property is required from the viewpoint of deterioration of the contents and functional deterioration.

[0027]

The present invention will be described below with reference to examples.
The present invention is not particularly limited to the following examples. (Measuring method)

The color difference b value in the present invention means the b value when measured by the Hunter Lab color system using a colorimetric color difference meter (ZE2000 manufactured by Nippon Denshoku Co., Ltd.) according to the JIS K8722 method. In general, the larger the b value, the tighter the yellow tint. The standard whiteboard (tristimulus value Y = 9
4.09, X = 92.19, Z = 110.78) were used. In the present invention, sampling was performed from a predetermined position in the roll in a state where four sheets were overlapped from the film roll, and the substrate film surface (anti-deposition surface) was directed to the light source side in the state where four sheets were stacked as it was and measured by a transmission method. The b value at that time was used.

The oxygen permeability referred to in the present invention is JIS K7126B.
Oxygen permeability measurement device (OXCON-2 /
20) was used and the temperature was 23 ° C. and the humidity was 65% RH. The water vapor permeability was measured using a water vapor permeability measuring device (PERMATRAN-W3 / 31 manufactured by US MOCON Co., Ltd.) according to JIS K7129B method under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. However,
Using a biaxially stretched polyamide film as the base film,
In addition, only those having no heat-sealable resin layer laminated were measured at a temperature of 23 ° C. and a humidity of 65% RH.

(Example 1) A biaxially stretched polyester film roll (product name E5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm and a total width of 2000 mm was attached to the unwinding side of the roll film in a take-up type vacuum vapor deposition machine and attached to a cooling drum After winding and passing the paper to the winding side, the chamber lid was closed and the pressure was reduced to the level of 10 ⁻⁴ Pa. Aluminum oxide and silicon oxide contained in a carbon crucible directly below the cooling drum were heated and evaporated by scanning an electron beam with an electron gun. When the pressure near the crucible became stable, the film running speed was accelerated to 150 m / min and the shutter was opened. A binary inorganic oxide film consisting of aluminum oxide and silicon oxide was measured on a polyester film with an in-line fluorescent X-ray monitor to obtain an average film thickness of 2
Vapor deposition was performed while finely adjusting the electron gun output so that the weight ratio of Al element: Si element was 1: 1 at 0 nm. Traveling speed
After winding 5000 m at 150 m / min, the shutter was closed, the output of the electron gun was stopped, and the film running was stopped. The inside of the vacuum vapor deposition machine was returned to atmospheric pressure, the vapor-deposited film roll was taken out, attached to the unwinding side of the slitter equipment, and passed through the winding side. The film path line from the film unwinding point to the film winding point is about 2 m, and the film is in contact with air except where it contacts several rolls. Room temperature 25 degrees, relative humidity 60% RH (absolute humidity approx.
0.012kg / kg) reaching the slitter winding side while slitting the film in a constant temperature and constant temperature environment Line traveling speed 200m / m
in rolled up. This slit vapor deposition film roll was stored in a constant temperature bath at 30 ° C. for 7 days to prepare a gas barrier film roll.

Example 2 A gas barrier film roll was prepared in the same manner as in Example 1 except that the slit vapor deposition film roll was stored in a constant temperature bath at 40 ° C. for 7 days.

(Example 3) A gas barrier film roll was prepared in the same manner as in Example 1 except that the slit vapor deposition film roll was stored in a constant temperature bath at 30 ° C for 14 days.

(Example 4) As a base film roll,
A gas barrier film roll was prepared in the same manner as in Example 1 except that an aqueous dispersion of an acrylic acid-containing polyester resin was used as a vapor deposition anchor layer for in-line coating at the time of film formation, and a biaxially stretched polyamide film roll having a total width of 2000 mm and a thickness of 15 μm was used.

(Embodiment 5) A thermostatic bath at 30 ° C. of Embodiment 1 is used.
A polyethylene film (L6102 40 μm manufactured by Toyobo Co., Ltd.) was laminated on the vapor deposition surface side by a dry lamination method on a gas barrier film roll after storage for a day to obtain a laminate. As the adhesive and the curing agent, TM590 and CAT56 manufactured by Toyo Morton Co., Ltd. were used and stored at 40 ° C. for 2 days to accelerate the curing of the adhesive.

Example 6 A gas barrier film roll, which had been stored for 7 days in a constant temperature bath at 30 ° C. of Example 1, was printed by a gravure printing method with a pattern including a printed portion and a plain portion on the vapor deposition surface. Ink used is New LP manufactured by Toyo Ink Co., Ltd.
Super white was used. Then, a laminate in which a polyethylene film was dry laminated on the printed surface was prepared in the same manner as in Example 5.

EXAMPLE 7 Toyo Morton EL530A and EL530B were used as anchor coating agents for the gas barrier film roll after being stored in the constant temperature bath of 30 ° C. of Example 1 for 7 days, and the vapor deposition surface side was formed by the extrusion lamination method. Polyethylene resin layer (Sumitomo Chemical Co., Ltd. Sumikasen L705
The laminated body was prepared by laminating 20 μm thick.

(Comparative Example 1) Example 1 except that the vapor-deposited film roll taken out from the vapor deposition machine was stored in a constant temperature bath at 30 ° C for 7 days in the roll state taken out from the vapor deposition machine without slitting. A gas barrier film roll was prepared in the same manner as in 1.

(Comparative Example 2) Room temperature 20 ° C, relative humidity 40% RH
A gas barrier film roll was prepared in the same manner as in Example 1 except that the film was slit and wound on the slitter winding side in a constant temperature and constant temperature environment (absolute humidity about 0.006 kg / kg).

Comparative Example 3 The film roll was immediately unwound without storing the slit vapor deposition film roll in a constant temperature bath and the physical properties such as gas barrier property and color difference were evaluated.

(Comparative Example 4) A gas barrier film loam prepared in the same manner as in Example 1 was tried to be wound, except that the slit vapor deposition film roll was stored in a constant temperature bath at 70 ° C, but the films were blocked. There was a partial state that impaired practicality.

(Comparative Example 5) As a base film roll, a biaxially stretched polyamide film roll having a thickness of 15 μm and a total width of 2000 mm, which was coated in-line with a water-dispersed coating agent of acrylic acid-containing polyester resin as a vapor deposition anchor layer, was used. A film roll prepared in the same manner as in Example 1 except that the temperature was 30 ° C. and the relative humidity was 80% RH (absolute humidity about 0.02).
Attempting to wind the film on the slitter winding side while slitting the film in a constant temperature and constant temperature environment of 2 kg / kg, the winding wrinkles due to moisture absorption occurred and impaired the practical quality.

The film rolls of Examples 1 to 4 and Comparative Examples 1 to 3 cut out from the surface layer portion and the intermediate portion in the lengthwise direction, and the oxygen permeability and the water vapor permeability of the edge portion with respect to the width direction, The measurement results of the color difference b value are shown in Table 1. Table 2 shows the oxygen permeability and water vapor permeability of the film pieces cut out from the laminates of Examples 5 to 7.

[0043]

[Table 1]

[0044]

[Table 2]

As is clear from the above Examples and Comparative Examples, a gas barrier film roll having a gas barrier thin film made of an inorganic oxide vapor-deposited on at least one side of a substrate roll film by a roll-up type vacuum vapor deposition method was used. 0.
After rewinding in an environment of 008-0.018kg / kg, 30-60 ℃
By storing in the above constant temperature environment for a certain period of time or more, the gas barrier property and the transparency can be uniformly improved over the entire length direction and the width direction. Also, excellent gas barrier properties and transparency can be obtained in a laminate obtained by laminating the gas barrier film roll and the heat sealable resin layer.

[0046]

As described above, the gas barrier film roll according to the present invention has a gas barrier thin film made of an inorganic oxide vapor-deposited on at least one side of a substrate roll film by a winding-type vacuum vapor deposition method and has an absolute humidity of 0.008 to 0.018. kg/
After rewinding in a state where the deposition surface is in contact with air under the environment of kg, by storing in a constant temperature environment of 30 to 60 ° C. for a certain period or longer, the gas barrier property and the transparency in the longitudinal direction,
It is intended to provide a film which is uniformly improved in the width direction and has excellent properties as various packaging materials. Further, the same effect can be obtained in a laminate laminated with a heat-sealing resin layer using the gas barrier film roll of the present invention, and a packaging bag using the laminate can obtain a packaging material with little variation in characteristics. .

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 14/08 C23C 14/08 K // C08L 101: 00 C08L 101: 00 F term (reference) 3E064 BA36 BA54 BB03 BC08 BC18 3E086 AA23 AC07 AD01 BA04 BA13 BA15 BA33 BB02 BB05 BB21 BB51 BB62 BB90 CA01 CA28 CA31 DA08 4F006 AA12 AA17 AA19 AA35 35 EJ98 GB15 HB31E JD02 JL12D YY00 4K029 AA11 AA25 BA50 BC00 BD00 EA08 GA03

Claims (7)

[Claims] 1. A gas barrier film roll obtained by vapor-depositing a gas barrier thin film layer made of an inorganic oxide on at least one side of a substrate film by a roll-up vacuum vapor deposition method, the gas barrier film roll being taken out from a vacuum vapor deposition apparatus, and having an absolute humidity. Is 0.008 to 0.018 kg / kg in an environment, the vapor deposition surface is rewound at least once in contact with air in the environment, and then stored in a roll at a constant temperature of 30 to 60 ° C. for a certain period or more, Also, the gas barrier film roll is characterized in that the color difference b value in a state where four films cut out from the roll after storage are stacked is within ± 3.0 in the width direction and the length direction of the roll. 2. A gas barrier film roll, wherein the gas barrier thin film layer comprising the inorganic oxide according to claim 1 is a composite oxide containing at least aluminum metal oxide and silicon oxide. 3. A gas barrier film roll, wherein the base film according to claim 1 is either a biaxially stretched polyamide film or a biaxially stretched polyester film. 4. A gas barrier film roll having a vapor deposition anchor layer between the substrate film according to claim 1 and the gas barrier thin film layer. 5. The gas barrier film roll according to any one of claims 1 to 4, wherein a heat-sealing resin layer is laminated on the gas barrier thin film layer via an anchor coating agent layer or an adhesive layer. 6. The laminate according to claim 5, wherein a print layer is first provided on the gas barrier thin film layer, and then a heat-sealable resin layer is laminated via an anchor coat agent layer or an adhesive layer. And a laminate. 7. A packaging bag, characterized by using the laminate according to claim 5 or 6 to heat-seal a heat-sealable resin layer to produce a bag.