JP2007216504A - Gas-barrier laminated film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier laminated film which is good in gas-barrier properties and superior in flexibility and keeps the good gas-barrier properties even after bag making, molding, packing, and sterilization processes. <P>SOLUTION: In the gas-barrier laminated film, an inorganic oxide vapor deposition film 2 is formed on a substrate 1, and a gas-barrier coating film 3 is formed on the vapor deposition film. The Young's modulus of the gas-barrier coating film is 15-40 MPa. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminated film having gas barrier properties and a method for producing the same. More specifically, the present invention has a gas barrier laminate film having a high gas barrier property and excellent flexibility, and maintaining a high gas barrier property even after steps such as bag making, molding, filling, and sterilization. It relates to the manufacturing method.

As a packaging material having a gas barrier property, a packaging material in which an aluminum foil layer is provided on a base material has been conventionally used. However, although such a packaging material has a stable gas barrier property, since it has an aluminum foil layer as a barrier layer, incineration suitability is inferior and disposal after use is not easy. Moreover, since the aluminum foil layer was provided, there also existed a problem that the packaging material which has transparency could not be obtained.
In order to solve such problems, packaging materials having a barrier layer made of polyvinylidene chloride (PVDC) or ethylene-vinyl alcohol copolymer (EVOH) have been developed.

  However, since PVDC contains chlorine, incineration after use generates chlorine gas, which is not preferable for environmental hygiene. On the other hand, EVOH has the advantage of high oxygen gas barrier properties and low flavor component adsorptivity, but has a problem that the oxygen gas barrier properties are reduced in a high humidity atmosphere. In addition, EVOH has a problem that it does not have a water vapor barrier property. For this reason, in order to shield EVOH which is a barrier layer from water vapor | steam, it is necessary to make a packaging material into a complicated laminated structure, and the problem that manufacturing cost increases may also arise.

  In recent years, a film having a barrier layer made of an inorganic oxide thin film such as silicon oxide or aluminum oxide has been developed as a packaging material that stably exhibits high gas barrier properties and fragrance retention properties and has transparency. . This inorganic oxide thin film is formed by depositing an inorganic substance on a substrate by vacuum vapor deposition, has no environmental problems at the time of disposal, and has no humidity dependency of gas barrier properties.

  However, since the barrier layer made of a thin film such as silicon oxide or aluminum oxide formed in this way is formed by depositing inorganic oxide particles on a substrate, a crystal grain boundary is formed between the inorganic oxide particles. There are gaps, and the gas barrier properties of the thin film are not sufficient. Therefore, it is necessary to increase the film thickness (500 to 1000 mm). However, when the film thickness is increased, there is a problem that the spreadability is poor and cracks are likely to occur.

  In addition, the smaller the oxygen atom ratio of the inorganic oxide, the better the gas barrier properties. However, on the other hand, there are various problems such as a problem that the transparency is lowered and the adhesion between the substrate and the inorganic oxide particles is weak. there were.

  Further, a barrier film obtained by depositing an inorganic oxide on a base material is not usually used alone as a packaging container or packaging material, and a printed layer, a laminate adhesive layer, a heat-sealable resin layer, etc. In addition, it becomes a package through various processes such as processing into a shape as a package, but the barrier film described above is inferior in flexibility, so oxygen permeability and water vapor The characteristics deteriorate greatly. In addition, the contents are filled and boiled and retort sterilized after the package is completed. However, gas barrier properties are reduced due to external addition, heat, and moisture in the process, and the base material and the inorganic oxide layer are separated ( There was a problem of delamination).

  In order to solve such problems related to gas barrier properties, various means have been proposed so far. For example, Patent Document 1 discloses that “a vapor deposition layer made of an inorganic compound is used as a first layer on a base material made of a polymer resin composition, and a water-soluble polymer and (a) one or more alkoxides and / or the same. A gas barrier film formed by applying an aqueous solution containing at least one of hydrolyzate or (b) tin chloride, or a water / alcohol mixed solution as a main ingredient and heating and drying is laminated as a second layer. A gas barrier laminate film characterized in that

  Although patent document 1 is disclosing laminating | stacking a gas-barrier film on a vapor deposition layer, about the softness | flexibility of a gas-barrier film which becomes a problem in the process process to a package, and the process process after a process. No consideration has been given. As a result, in the invention described in Patent Document 1, the Young's modulus of the gas barrier coating is not defined at all. Furthermore, in the production of the gas barrier laminate film described in Patent Document 1, since the coating is applied and dried at a temperature as low as 120 ° C., the water-soluble polymer polymer does not sufficiently crosslink, and a part of the hydroxyl groups are not formed. It remains in the film. As a result, the crosslinking is broken by moisture, the barrier property of the gas barrier coating layer is deteriorated, or the adhesion between the inorganic compound layer and the gas barrier coating layer interface is lowered. In addition, there is a problem that the gas barrier coating layer is cracked by an external load such as bending, stretching, etc. in printing, laminating, bag making, filling, boil / retort sterilization process, and the barrier property is lowered.

  Patent Document 2 states that “polycondensation of a coating composition containing a metal alkoxide or a hydrolyzate thereof and an ethylene / vinyl alcohol copolymer via an inorganic thin film layer on at least one surface of a base film of a thermoplastic resin. A gas barrier laminate film having a composite polymer layer formed as described above is described.

  Although Patent Document 2 discloses providing a composite polymer layer on an inorganic thin film layer, the Young's modulus of the composite polymer layer is not defined at all. Therefore, there is a problem that the gas barrier coating layer is cracked by an external load such as bending, stretching, etc. in printing, laminating, bag making, filling, boil / retort sterilization process, and the barrier property is lowered.

  Further, Patent Document 3 states that “at least one surface of a base film has a coating layer formed by a reaction between an organic chain-containing both-end functional silane monomer and a silane compound via an inorganic thin film layer. Barrier composite film "is described.

  The invention described in Patent Document 3 provides barrier properties, adhesion between layers, and transparency by providing a coating layer formed by a reaction between an organic chain-containing both-end functional silane monomer and a silane compound on an inorganic thin film layer. However, the Young's modulus of the coating layer is not defined at all. Furthermore, in the production of the gas barrier laminated film described in Patent Document 3, the coating layer is formed by natural drying or at a temperature as low as 100 ° C. Therefore, in the printing, laminating, bag making, filling, and boil / retort sterilization processes. There is a problem that a crack is generated in the coating layer due to an external load such as bending and stretching, and the barrier property is lowered.

In the invention described in Patent Document 3, an organic chain-containing both-end functional silane monomer, that is, a functional group having an organic chain in the molecular chain and silicon atoms bonded to both ends is used for forming the coating layer. Although the reactivity of this organic chain-containing both-end functional silane monomer and the silane compound is very high, and the by-product generated by this reaction is trapped in the film, It cannot be sufficiently removed by drying, and the solvent remains in the film. Furthermore, since the coating layer formed in the invention of Patent Document 3 is rough, it cannot obtain a sufficient water vapor barrier property.
Japanese Patent No. 2790054 JP 2000-71396 A JP 2001-191445 A

  As described above, the gas barrier laminate film is required to have high barrier properties, and to have excellent flexibility that does not deteriorate the gas barrier properties in bag making, molding, filling, sterilization processes, and the like. However, a gas barrier laminate film having such characteristics has not been obtained.

  In contrast, the present invention provides a gas barrier laminate film that has high gas barrier properties and excellent flexibility, and maintains high gas barrier properties even after bag making, molding, filling, sterilization, and the like. To do.

As a result of intensive studies to solve the above problems, the present inventors have made the Young's modulus of the gas barrier coating film formed on the inorganic oxide deposited on the base material specific and compared it with the conventional one. In addition, a gas barrier laminated film having high gas barrier properties and excellent flexibility, that is, no damage such as cracks occurs in the gas barrier coating film due to bag making processing, molding processing, etc., and a high gas barrier even after the processing. The present invention has been completed by finding that the specific Young's modulus can be achieved by controlling the heat treatment temperature and time during the formation of a gas barrier coating film and obtaining a gas barrier laminated film that maintains the properties.
That is, the present invention includes the inventions shown in the following (a) and (b).
(A) a gas barrier laminate film in which a vapor-deposited film of an inorganic oxide is provided on a substrate, and a gas-barrier coating film is provided on the vapor-deposited film,
A gas barrier laminate film, wherein the gas barrier coating film has a Young's modulus of 15 MPa to 40 MPa.
(B) A method for producing the gas barrier laminate film of (a) above,
Form a vapor-deposited film of inorganic oxide on the substrate,
A method comprising applying a gas barrier coating liquid on the vapor-deposited film and forming the gas barrier coating film by heating at a temperature of 150 to 250 ° C. for 1 second to 2 minutes.

  Since the gas barrier coating film of the gas barrier laminate film of the present invention has the specific Young's modulus, it has high gas barrier properties and excellent flexibility. That is, according to the present invention, the gas barrier coating film is not damaged by cracking or the like even after bag making, molding, filling, sterilization, etc., and the gas barrier property that maintains high gas barrier properties even after the processing step. A laminated film can be provided.

The gas barrier laminate film of the present invention will be described in detail with reference to the drawings.
1 and 2 are schematic cross-sectional views showing an example of the layer structure of the gas barrier laminate film of the present invention.

  As shown in FIG. 1, the gas barrier laminate film of the present invention performs a surface treatment of a substrate on one surface of a substrate film 1, and provides an inorganic oxide vapor deposition film 2 on the treated surface 1a. The basic structure is a structure in which a gas barrier coating film 3 is provided on the inorganic oxide vapor-deposited film 2.

  As another aspect of the gas barrier laminate film of the present invention, as shown in FIG. 2, a primer coat layer 1b is provided on one surface of a base film 1, and an inorganic oxide vapor deposition film 2 is provided on the primer coat layer. In addition, the basic structure is a structure in which a gas barrier coating film 3 is provided on the inorganic oxide vapor deposition film 2.

  Here, the Young's modulus of the gas barrier coating film must be 15 to 40 MPa, desirably 15 to 30 MPa, more preferably 15 to 25 MPa, and particularly preferably 18 to 22 MPa. By making the Young's modulus of the gas barrier coating film in the above specified range, the gas barrier property of the gas barrier laminated film itself is improved, and damage such as cracks does not occur due to bag making processing or molding processing. A gas barrier laminate film that maintains high gas barrier properties can be obtained.

When the Young's modulus of the gas barrier coating film is less than 15 MPa, the gas barrier properties such as oxygen permeability and water vapor permeability of the gas barrier laminated film itself are lowered, and cracks are generated due to bag making processing and molding treatment. Sex is reduced. On the other hand, if the Young's modulus of the gas barrier coating film exceeds 40 MPa, sufficient flexibility cannot be obtained, and cracking occurs due to bag making processing or molding processing, resulting in a problem that the gas barrier property is lowered.
The Young's modulus of the above gas barrier coating film is that the gas barrier coating liquid is applied onto the inorganic oxide deposited film deposited on the substrate, and then heat-treated at a temperature of 150 to 250 ° C. for 1 second to 2 minutes. Can be achieved.

The Young's modulus referred to in the present invention is the amount of displacement of the laminated film to be measured at 25 ° C. (when one end in the longitudinal direction of the film is fixed and the opposite end is the free end, the fixed end and the free end are Height difference), film length, width, thickness of each layer, layer density of each layer, bending moment of inertia of each layer, and calculated using the following formula.
X = {- b × Σ ( h × d / 2) × 3L 4/12} / Σ (E × Iy)
(Where X is the displacement of the laminated film to be measured, L and b are the length and width of the film, h is the thickness of each layer in the film, d is the layer density of each layer in the film, Iy represents the moment of inertia of bending of each layer in the film.)
Said example is an example of the gas barrier laminated film of this invention, and this invention is not limited to this.
For example, although not illustrated, in the laminated film of the present invention, the inorganic oxide vapor deposition film may be formed by stacking two or more inorganic oxide vapor deposition films of the same type or different types.

Next, the material which comprises the gas barrier laminated film of this invention, its manufacturing method, etc. are demonstrated.
Substrate The substrate constituting the gas barrier laminate film of the present invention is excellent in chemical or physical strength, withstands the conditions for forming an inorganic oxide vapor-deposited film, and the properties of the inorganic oxide vapor-deposited film, etc. It is possible to use a resin film or sheet that can be satisfactorily held without impairing the resistance.

Specific examples of such a resin film or sheet include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, and acrylonitrile-styrene copolymers (AS resins). , Acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as various nylons, polyurethane resin Further, films or sheets of various resins such as acetal resin and cellulose resin can be used.

  In the present invention, among the above-described resin films or sheets, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

  In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, etc. are manufactured. Using the film forming method, the above-mentioned various resins are formed into a single film, or two or more types of various resins are used to form a multi-layer coextrusion film, and further, two or more types of resin are formed. Resin is used, and various resin films or sheets are manufactured by a method of forming a film by mixing before forming a film, and further, for example, a tenter method or a tube llama method can be used. Various resin films or sheets stretched uniaxially or biaxially by use can be used.

  In the present invention, the film thickness of various resin films or sheets is preferably 6 to 200 μm, more preferably 9 to 100 μm.

  In addition, when using one or more of the above-described various resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose.

  In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. In this case, a modifying resin or the like can also be used.

  In addition, in the present invention, the surface of various resin films or sheets may be provided with a desired surface treatment layer in advance, if necessary, in order to improve close adhesion with an inorganic oxide vapor deposition film. It can be done.

  In the present invention, examples of the surface treatment layer include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, and the like. For example, a corona discharge treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed by performing pretreatment arbitrarily.

  The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and the inorganic oxide vapor-deposited film. For example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a deposition anchor coat agent layer is arbitrarily formed in advance on the surface of various resin films or sheets. The surface treatment layer can also be used.

  Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition containing a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used. In particular, it is preferable to use a coating agent comprising polyester, acrylic, urethane resin, and isocyanate curing agent as the primer coating agent.

Deposited film will now be described deposited film constituting the gas barrier laminate film of the present invention. In the present invention, the deposited film can be formed by chemical vapor deposition or physical vapor deposition.

Formation of vapor-deposited film by chemical vapor deposition As chemical vapor deposition , specifically, for example, chemical vapor deposition such as plasma chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition A vapor deposition film of an inorganic oxide can be formed using (Chemical Vapor Deposition method, CVD method).

  More specifically, on one surface of the resin film or sheet, an evaporation monomer gas such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen Can be used as a supply gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed by a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.

  In the above, as the low-temperature plasma generator, for example, generators such as high-frequency plasma, pulse wave plasma, microwave plasma can be used, but in the present invention, in order to obtain a highly active stable plasma, It is desirable to use a high frequency plasma generator.

  Specifically, an example of the method for forming a vapor-deposited film of an inorganic oxide by the plasma chemical vapor deposition method will be described. FIG. 3 is a schematic configuration diagram of a low-temperature plasma chemical vapor deposition apparatus showing the outline of the method for forming a deposited film of an inorganic oxide by the plasma chemical vapor deposition method.

  As shown in FIG. 3, in the present invention, a resin film or sheet is fed out from an unwinding roll 23 disposed in the vacuum chamber 22 of the plasma chemical vapor deposition apparatus 21, and further, the resin film or sheet is It is conveyed on the circumferential surface of the cooling / electrode drum 25 through the auxiliary roll 24 at a predetermined speed.

  In the present invention, vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound or the like is supplied from the gas supply devices 26 and 27 and the raw material volatilization supply device 28, and a mixed gas composition for vapor deposition composed thereof is prepared. Then, the gas mixture composition for vapor deposition is introduced into the vacuum chamber 22 through the raw material supply nozzle 29, and the glowing film is formed on the resin film or sheet conveyed on the cooling / electrode drum 25 peripheral surface. Plasma is generated by discharge plasma and irradiated to form a vapor-deposited film of an inorganic oxide such as silicon oxide to form a film.

In the present invention, a predetermined power is applied to the cooling / electrode drum 25 from the power supply 31 arranged outside the chamber at that time, and a magnet 32 is provided in the vicinity of the cooling / electrode drum 25. And the generation of plasma is promoted, and then the resin film or sheet on which the deposited film of inorganic oxide such as silicon oxide is formed is wound around the winding roll 34 via the guide roll 33, A resin film or sheet having an inorganic oxide vapor deposition film can be produced.
The above exemplification is an example, and the present invention is not limited thereby.

In the present invention, the inorganic oxide vapor-deposited film may be not only one layer of the inorganic oxide vapor-deposited film but also a multilayer film in which two or more layers are laminated, and one kind of material is used. Alternatively, it is also possible to form a vapor-deposited film of an inorganic oxide that is used in a mixture of two or more kinds and mixed with different materials.
In the above, the inside of the vacuum chamber is depressurized by a vacuum pump, and the degree of vacuum is 1.33 × 10 ^−1.
˜1.33 × 10 ⁻⁸ mbar, preferably 1.33 × 10 ^{−3 to} 1.33 × 10 ⁻⁷ m
It is preferable to adjust to bar.

  Further, in the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is passed through the raw material supply nozzle in the vacuum chamber. To introduce.

  In this case, the content of the organosilicon compound in the mixed gas can be 1 to 40%, the content of oxygen gas can be 10 to 70%, and the content of inert gas can be 10 to 60%. The mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be 1: 6: 5 to 1:17:14.

  On the other hand, since a predetermined voltage is applied to the cooling / electrode drum from the electrode, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The plasma is derived from one or more gas components in the mixed gas. In this state, the resin film or sheet is transported at a constant speed, and a glow discharge probe is used to cool and cool the electrode drum surface. A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed on a resin film or sheet.

The degree of vacuum in the vacuum chamber at this time is 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻⁴ mbar, preferably 1.33 × 10 ^{−1 to} 1.33 × 10 ^−2. It is preferable to adjust to mbar, and the conveyance speed of the resin film is preferably adjusted to 10 to 300 m / min, and preferably 50 to 150 m / min.

  In the plasma chemical vapor deposition apparatus described above, the formation of a vapor-deposited film of an inorganic oxide such as silicon oxide is performed in the form of SiOx while oxidizing a plasma source gas with oxygen gas on a resin film or sheet. Therefore, the formed vapor-deposited film of inorganic oxide such as silicon oxide is a dense continuous layer having a small gap and rich in flexibility. Therefore, the gas barrier property of the vapor-deposited film of inorganic oxide such as silicon oxide is much higher than that of the vapor-deposited film of inorganic oxide such as silicon oxide formed by the conventional vacuum vapor deposition method or the like. Can provide sufficient gas barrier properties.

  In the present invention, the surface of the resin film or sheet is cleaned by SiOx plasma, and polar groups, free radicals, etc. are generated on the surface of the resin film or sheet. It has the advantage that the tight adhesion between the inorganic oxide vapor-deposited film and the resin film or sheet is high.

Further, as described above, the degree of vacuum when forming a continuous film of inorganic oxide such as silicon oxide is 1.33.
× 10 ^{−1 to} 1.33 × 10 ⁻⁴ mbar, preferably 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻²
Since the pressure is adjusted to mbar, the degree of vacuum (1.33 ×
10 ^{-4 to} 1.33 × 10 ^-5 mbar), the vacuum state setting time can be shortened when the raw film is replaced with a resin film or sheet, and the degree of vacuum is stable. In addition, the film forming process is stable.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It is closely bonded to one surface of a resin film or sheet to form a dense, flexible thin film, and is generally represented by the general formula: SiOx (wherein x represents a number from 0 to 2) Is a continuous thin film mainly composed of silicon oxide.

  The silicon oxide vapor-deposited film is made of silicon oxide represented by the general formula: SiOx (wherein x represents a number of 1.3 to 1.9) from the viewpoint of transparency and barrier properties. A thin film mainly composed of a deposited film is preferable.

  In the above, the value of x varies depending on the molar ratio of vapor deposition monomer gas to oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of x decreases, but the film itself is yellow. It becomes sexual and becomes less transparent.

  The silicon oxide vapor-deposited film is mainly composed of silicon oxide, and in addition to this, at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements thereof is chemically bonded. Etc. are preferably contained. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, an organic silicon compound as a raw material or a derivative thereof is further added. It may be contained by a chemical bond or the like.

Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.

  In addition to the above, the type, amount, etc., of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process.

As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, about 0.1 to 50%,
Preferably, about 5 to 20% is preferable.

  In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending, It becomes difficult to stably maintain a high barrier property, and if it exceeds 50%, the gas barrier property is lowered, which is not preferable.

  Further, in the present invention, in the silicon oxide vapor-deposited film, the content of the above compound is preferably decreased from the surface of the silicon oxide vapor-deposited film in the depth direction, whereby the silicon oxide vapor-deposited film is formed. On the other hand, the impact resistance and the like can be enhanced by the above compound and the like, and on the other hand, since the content of the above compound is small at the interface with the base material, the tight adhesion between the base material and the deposited silicon oxide film is strong. It will be something.

  In the present invention, for the above-described deposited film of silicon oxide, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS) or a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS) is used. The physical properties as described above can be confirmed by performing elemental analysis of the deposited film of silicon oxide using a method of analysis by ion etching in the depth direction.

  Further, in the present invention, the film thickness of the above-described silicon oxide vapor deposition film is preferably 50 to 4000 mm, and specifically, the film thickness is preferably 100 to 1000 mm. If the thickness is more than 1000 mm, and more than 4000 mm, cracks and the like are likely to occur in the film, which is not preferable. If the thickness is less than 100 mm, and less than 50 mm, the gas barrier effect cannot be expected.

  The film thickness of the deposited film can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation.

  In addition, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas or the method of slowing the vaporization rate. Etc.

  Next, in the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl Trimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like can be used.

  In the present invention, among the above organosilicon compounds, the use of 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle, and a continuous film formed. In view of the above characteristics and the like, it is a particularly preferable raw material.

  Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

  In the present invention, when forming a vapor deposition film by chemical vapor deposition, it is preferable to form two or more silicon oxide layers. Thus, gas barrier properties can be further improved by providing two or more deposited layers.

  Next, a method for producing two or more deposited films by plasma chemical vapor deposition will be described. As shown in FIG. 4, the plasma chemical vapor deposition apparatus 40 basically includes a base film supply chamber 41, a first film forming chamber 42, a second film forming chamber 43, and a third film forming chamber 44. And a winding chamber 45 for winding a film in which a silicon oxide layer is formed on a base film and stacked.

  First, the base film 1 wound around the unwinding roll 46 is fed out to the first film forming chamber 42, and this base film 1 is further cooled at a predetermined speed via the auxiliary roll 47 and the electrode drum. Conveyed on 48 circumferential surfaces.

  Next, a film-forming monomer gas, oxygen gas, inert gas, or the like comprising at least one organic silicon compound is supplied from the raw material volatilization supply device 49 and the gas supply device 50, and a film-forming mixed gas composition comprising them. The mixed gas composition for film formation is introduced into the first film formation chamber 42 through the raw material supply nozzle 51, and the top of the substrate film 1 conveyed on the circumferential surface of the cooling / electrode drum 48 is adjusted. In addition, plasma is generated by the glow discharge plasma 52 and irradiated to form a first silicon oxide layer made of silicon oxide or the like.

  Next, the base film obtained by forming the first silicon oxide layer in the first film forming chamber 42 is fed out to the second film forming chamber 43 through the auxiliary rolls 53 and 54, and then In the same manner as described above, the base film on which the first silicon oxide layer is formed is transported onto the peripheral surface of the cooling / electrode drum 55 at a predetermined speed.

  Thereafter, in the same manner as described above, a film-forming monomer gas, oxygen gas, inert gas, or the like made of one or more organic silicon compounds is supplied from the raw material volatilization supply device 56 and the gas supply device 57, and the film-forming film made of them. While adjusting the mixed gas composition, the film-forming mixed gas composition is introduced into the second film-forming chamber 43 through the raw material supply nozzle 58, and is conveyed onto the cooling / electrode drum 55 peripheral surface. A plasma is generated by glow discharge plasma 59 on the first silicon oxide layer of the base film obtained by forming the first silicon oxide layer, and is irradiated with the silicon oxide. A second silicon oxide layer made of, for example, is formed.

  Further, in the same manner as described above, the base film obtained by forming the first layer and the second silicon oxide layer in the second film forming chamber is formed into the third film through the auxiliary rolls 60 and 61. Then, the substrate film is fed into the chamber 44, and then the base film formed by forming the first layer and the second layer of silicon oxide is transported onto the peripheral surface of the cooling / electrode drum 62 at a predetermined speed in the same manner as described above.

  Thereafter, in the same manner as above, a film-forming monomer gas, oxygen gas, inert gas, or the like composed of one or more organic silicon compounds is supplied from the raw material volatilization supply device 63 and the gas supply device 64, and a film is formed of these. The above mixed gas composition for film formation is introduced into the third film forming chamber 44 through the raw material supply nozzle 65 while adjusting the mixed gas composition for cooling, and is conveyed onto the cooling / electrode drum circumferential surface. Plasma is generated by glow discharge plasma 66 on the second silicon oxide layer of the base film obtained by forming the first and second silicon oxide layers, and this is irradiated. A third silicon oxide layer made of silicon oxide or the like is formed.

  Next, the silicon oxide layers of the first layer, the second layer, and the third layer are formed as described above, and the base film on which these layers are stacked is fed to the winding chamber 45 through the auxiliary roll 67, and then The gas barrier laminate film having a vapor deposition layer in which the first layer, the second layer, and the third silicon oxide layer are overlaid can be manufactured by being wound on a winding roll 68.

  In the present invention, each cooling / electrode drum (48, 55, 62) disposed in each of the first, second and third film forming chambers (42, 43, 44) A predetermined power is applied from a power source 69 disposed outside the second and third film forming chambers, and in the vicinity of each cooling / electrode drum (48, 55, 62), Magnets (70, 71, 72) are arranged to promote the generation of plasma.

  Although not shown, the plasma chemical vapor deposition apparatus is provided with a vacuum pump and the like, and each film forming chamber is adjusted to be kept in vacuum.

  The above illustration is an example of the present invention, and the present invention is not limited thereby. In the above example, a gas barrier laminated film in which the first layer, the second layer, and the third layer silicon oxide layer are overlaid is manufactured. Then, for example, a silicon oxide layer such as two layers or four or more layers can be arbitrarily formed and formed into a layered structure. The present invention is not limited only to the example of manufacturing a gas barrier laminate film in which the first, second, and third silicon oxide layers are overlaid.

In the above, each film forming chamber is depressurized by a vacuum pump or the like, and the degree of vacuum is 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻⁸ mbar, preferably, the degree of vacuum is 1.33 × 10 ⁻³ to 1. It is preferable to adjust to 33 × 10 ⁻⁷ mbar.

  On the other hand, since a predetermined voltage is applied to each cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in each film forming chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas composition for film formation. In this state, the base film is transported at a constant speed, and the glow discharge plasma is used to cool the electrodes. A silicon oxide layer made of silicon oxide or the like can be formed on the substrate film on the drum peripheral surface.

At this time, the degree of vacuum in each film forming chamber is 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻⁴ mbar, preferably 1.33 × 10 ^{−1 to} 1.33 × 10 ⁻ Adjust to ² mbar. Moreover, the conveyance speed of a base film is 10-300 m / min, Preferably, it adjusts to 50-150 m / min.

  In the present invention, the degree of vacuum in each film forming chamber may be the same or different in each chamber.

  In the raw material volatilization supply device, the monomer gas for film formation composed of one or more organic silicon compounds as raw materials is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and from these It is preferable that the film-forming mixed gas composition is introduced into each film-forming chamber via the raw material supply nozzle while adjusting the film-forming mixed gas composition.

  In this case, as the gas mixing ratio of each gas component of the film-forming mixed gas composition, the content of the monomer gas for film formation composed of one kind of organosilicon compound is 1 to 40%, and the content of oxygen gas is The content of the inert gas is preferably adjusted in the range of 1 to 60%.

  In the present invention, a film-forming mixed gas composition prepared by changing the gas mixing ratio of each gas component of the film-forming mixed gas composition introduced into each film-forming chamber is used for each film-forming chamber. It is preferable to form a film for each film forming chamber and to stack a silicon oxide layer made of silicon oxide or the like.

  That is, in the present invention, at least one film forming monomer gas, oxygen gas, and film forming gas containing mixed gas composition containing an inert gas is used. Two or more plasma chemical vapor phases using the mixed gas composition for film formation are prepared by using the mixed gas composition for film formation for each film forming chamber. A silicon oxide layer can be formed by a growth method.

  In the present invention, as the mixing ratio of each gas component of the film forming mixed gas composition, for example, as the first film forming mixed gas composition, the film forming monomer gas: oxygen gas: inert gas = 1. : A mixed gas composition for film formation having a gas composition ratio of 0 to 5: 1 (unit: slm, which is an abbreviation for standard liter minute), and another second mixed gas composition for film formation, Film forming monomer gas: oxygen gas: inert gas = 1: 6 to 15: 1 (unit: slm), and a film forming mixed gas composition having a gas composition ratio can be used.

  In the present invention, the mixed gas composition for film formation as described above is arbitrarily combined, and each gas component of the mixed gas composition for film formation is placed in the first, second, or third film forming chamber. It can be formed into a film by using a mixed gas composition for film formation with different mixing ratios.

Formation of Vapor Deposition Film by Physical Vapor Deposition Method In the present invention, the inorganic oxide vapor deposition film may be, for example, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or an ion cluster beam method.
Vapor Deposition method, PVD method).

Specifically, a metal oxide is used as a raw material, and this is heated to deposit on a resin film or sheet, or a metal or metal oxide is used as a raw material and oxygen is introduced. An amorphous thin film of inorganic oxide is formed using an oxidation reaction deposition method that oxidizes and deposits on a resin film or sheet, and a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma. can do.

  In the above, the heating method of the vapor deposition material can be performed by, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like.

  Examples of the deposited film of the inorganic oxide include a deposited film of a metal oxide. Specifically, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K ), Tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), etc. it can. Preferable examples include metals such as silicon (Si) and aluminum (Al).

  The deposited metal oxide film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide. The notation can be expressed by, for example, MOx such as SiOx, AlOx, and MgOx. (In the formula, M represents a metal element, and the value of x varies depending on the metal element).

  Moreover, as a range of said value of x, silicon (Si) is 0-2, aluminum (Al) is 0-1.5, magnesium (Mg) is 0-1, calcium (Ca) is 0-1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1 for boron (B), 0 to 2 for titanium (Ti). Lead (Pb) can take values in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5.

  In the above, when x = 0, it is a perfect metal and cannot be used because it is not transparent. In addition, the upper limit of the range of x is a completely oxidized value.

  In the present invention, silicon (Si) and aluminum (Al) are preferably used, and silicon (Si) has a value in the range of 1.0 to 2.0, and aluminum (Al) has a value in the range of 0.5 to 1.5. Things can be used.

  In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the type of metal or metal oxide used, but is, for example, about 50 to 4000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.

  In the present invention, the inorganic oxide vapor-deposited film is a metal to be used, or the metal oxide is one or a mixture of two or more, and mixed with different materials. It is also possible to form a deposited film.

  Next, in the present invention, a method for forming a vapor-deposited film of the above inorganic oxide will be described. FIG. 5 is a schematic configuration diagram illustrating an example of a take-up vacuum deposition apparatus.

  As shown in FIG. 5, in the winding chamber 81 of the winding type vacuum vapor deposition apparatus 80, the resin film or sheet 1 fed out from the unwinding roll 82 is cooled via the guide rolls 83 and 84. Guided to 85.

  The evaporation source 86 heated by the crucible 92, for example, metal aluminum or aluminum oxide is evaporated on the resin film or sheet guided on the cooled coating drum, and oxygen, if necessary. For example, an inorganic oxide vapor deposition film such as aluminum oxide is formed on a resin film or sheet through a mask 88 while oxygen gas or the like is jetted from the gas outlet 87 and supplied.

  Next, for example, a resin film or sheet on which an inorganic oxide vapor-deposited film such as aluminum oxide is formed is wound around a take-up roll 91 via guide rolls 89 and 90, and a resin having an inorganic oxide vapor-deposited film. The film or sheet can be produced.

The degree of vacuum of the take-up chamber is 10 ⁰ to 10 ⁻⁵ mbar, preferably 10 ⁻¹ to 10 ⁻⁴ mbar. Further, the degree of vacuum of the vapor deposition chamber is preferably 10 ⁻² to 10 ⁻⁸ mbar, preferably 10 ⁻³ to 10 ⁻⁷ mbar before introducing the oxygen gas, and is preferably 10 ⁻³ to 10 ⁻⁷ mbar after introducing the oxygen gas. ^-1 to 10 ^-6 mbar, preferably 10 ^-2 to 10 ^-5 mbar. Moreover, as a conveyance speed of a flexible plastic base material, 10-800 m / min, Preferably, 50-600 m / min is desirable.
The above exemplification is an example, and the present invention is not limited thereby.

  In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or the above-described winding type vacuum vapor deposition apparatus is used to connect the two in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form an inorganic oxide vapor-deposited film composed of two or more multilayer films.

  After forming a vapor-deposited film of an inorganic oxide on a substrate by chemical vapor deposition or physical vapor deposition as described above, the vapor-deposited film may be further subjected to glow discharge treatment, plasma treatment, or microwave treatment. Good. This further improves the adhesion between the deposited film and the following gas barrier coating film.

Gas barrier coating film Next, the gas barrier coating film constituting the gas barrier laminated film of the present invention will be described.
As the gas barrier coating film, a composition containing at least one alkoxide represented by the general formula: R ¹ _n M (OR ² ) _m , polyvinyl alcohol and / or ethylene / vinyl alcohol is polycondensed by a sol-gel method. A gas barrier coating film obtained from the gas barrier composition can be used.

The alkoxide that can be suitably used in the present invention has a general formula: R ¹ _n M (OR ² ) _m (wherein M is a metal atom, R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and n is 0 or more) , M represents an integer of 1 or more, and n + m represents a valence of M), and at least one kind of a partial hydrolyzate of alkoxide or a hydrolyzed condensate of alkoxide can be used. . In addition, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which one or more was hydrolyzed, and its mixture may be sufficient. Further, the hydrolysis condensate represents a dimer or more of a partially hydrolyzed alkoxide, and a 2-6 mer is usually used.

As the metal atom represented by M in the above general formula: R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum and the like can be used, and preferably silicon. These alkoxides can be used singly or as a mixture of two or more different metal atom alkoxides in the same solution.

Specific examples of the organic group R ¹ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n- Examples include alkyl groups such as hexyl group and n-octyl group. Specific examples of the organic group R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. These alkyl groups in the same molecule may be the same or different.

Among the alkoxides, an alkoxysilane in which M is Si is preferable, and the alkoxysilane is represented by Si (OR ^a ) ₄ , and R is a lower alkyl group. As R ^a , a methyl group, an ethyl group, an N-propyl group, an N · butyl group, or the like is used. Specific examples of alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂
H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) _{4 and the} like.

Further, alkylalkoxysilane R ^b _m Si (OR ^c ) _4-m can be used (m is an integer of 1, 2, 3). As R ^b and R ^c , a methyl group, an ethyl group or the like is used. Specific examples of the alkylalkoxysilane include methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H _{5) 3,} etc. dimethyldimethoxysilane _{(CH 3) 2 Si (OCH} 3) 2 dimethyldiethoxysilane _{(CH 3) 2 Si (OC} 2 H 5) 2 and the like. These alkoxysilanes and alkylalkoxysilanes can be used alone or in combination of two or more.

  Furthermore, polycondensation products of alkoxysilanes can be used, and specific examples include polytetramethoxysilane and polytetraemethoxysilane.

Among the alkoxides, specific examples of zirconium alkoxides in which M is Zr include tetramethoxyzirconium Zr (O—CH ₃ ) ₄ , tetraethoxyzirconium Zr (O—C ₂ H ₅ ) ₄ , tetraipropoxyzirconium Zr. _{(O-Iso-C 3 H} 7) 4, tetra-n-butoxy zirconium _{Zr (O-C 4 H 9} ) 4 and the like can be suitably used.

Among the above alkoxides, specific examples of titanium alkoxides in which M is Ti include tetramethoxytitanium Ti (O—CH ₃ ) ₄ , tetraethoxytitanium Ti (O—C ₂ H ₅ ) ₄ , and tetraisopropoxytitanium Ti. _{(O-Iso-C 3 H} 7) 4, tetra-n-butoxy titanium _{Ti (O-C 4 H 9} ) 4 and the like can be suitably used.

Among the alkoxides, specific examples of aluminum alkoxides in which M is Al include tetramethoxyaluminum Al (O—CH ₃ ) ₄ , tetraethoxyaluminum Al (O—C ₂ H ₅ ) ₄ tetraisopropoxyaluminum Al ( _{O-Iso-C 3 H 7} ) 4, tetra-n-butoxy aluminum _{Al (O-C 4 H 9} ) 4 and the like can be suitably used.

  Two or more kinds of these alkoxides may be mixed and used. In particular, by using a mixture of alkoxysilane and zirconium alkoxide, the toughness and heat resistance of the resulting laminated film can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. The amount of zirconium alkoxide used is in the range of 10 parts by weight or less, preferably about 5 parts by weight, based on 100 parts by weight of alkoxysilane. When the amount exceeds 10 parts by weight, the formed composite polymer is easily gelled, the brittleness of the composite polymer is increased, and the composite polymer layer is easily peeled off when the base film is coated.

  In particular, by using a mixture of alkoxysilane and titanium alkoxide, the thermal conductivity of the resulting coating is lowered, and the heat resistance of the substrate is significantly improved. The amount of titanium alkoxide used is in the range of 5 parts by weight or less, preferably about 3 parts by weight, based on 100 parts by weight of alkoxysilane. If the amount exceeds 5 parts by weight, the brittleness of the composite polymer formed becomes large, and the composite polymer is easily peeled off when the base film is coated.

In the present invention, a silane coupling agent is preferably used in combination with the alkoxide. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is suitable. Examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Two or more kinds of such silane coupling agents may be mixed and used. The amount of the silane coupling agent used is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. When 20 parts by weight or more is used, the composite polymer formed is increased in rigidity and brittleness, and the insulation and workability of the composite polymer layer are lowered.

  In the present invention, the composition (coating liquid) for forming a gas barrier coating film contains polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer. By combining polyvinyl alcohol and ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance and the like of the resulting coating film are remarkably improved. Furthermore, a laminated film in which polyvinyl alcohol and ethylene / vinyl alcohol copolymer are combined is excellent in hot water resistance and gas barrier property after hot water treatment in addition to gas barrier properties, water resistance, and weather resistance.

When the combination of polyvinyl alcohol and ethylene / vinyl alcohol copolymer is employed, the weight ratio of each is preferably 10: 0.05 to 10: 6, more preferably about 10: 1.

  The total content of the polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer is in the range of 5 to 600 parts by weight, preferably about 50 to 400 parts by weight, with respect to 100 parts by weight of the total amount of the alkoxide. If it exceeds 600 parts by weight, the brittleness of the composite polymer increases, and the water resistance and weather resistance of the resulting laminated film also deteriorate. When the amount is less than 5 parts by weight, the gas barrier property is lowered.

  In this invention, said composition (coating liquid) is apply | coated on a vapor deposition film | membrane, The composition is polycondensed by the sol-gel method, and a coating film is obtained. As the sol-gel catalyst, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, there are N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and NN-dimethylbenzylamine is particularly preferable. The amount used is 0.01 to 1 part by weight, preferably about 0.03 part by weight, per 100 parts by weight of the total amount of alkoxide and silane coupling agent.

  In the present invention, the above composition may contain an acid instead of the tertiary amine or further. The acid is used as a sol-gel catalyst, mainly as a catalyst for hydrolysis of alkoxides, silane coupling agents and the like. As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent.

In the present invention, the composition for forming a gas barrier coating film contains 0.1 to 100 moles, preferably 0.8 to 2 moles of water with respect to 1 mole of the total mole amount of alkoxide. Is preferred. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked to form a porous polymer having a low density. . The porous polymer cannot improve the gas barrier property of the base film. When the amount of water is less than 0.8 mol, the hydrolysis reaction hardly proceeds.

  Moreover, it is preferable that the composition for gas-barrier coating film formation contains an organic solvent. As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like are used.

  The polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer is preferably in a state of being dissolved in a composition (coating liquid) containing the alkoxide or silane coupling agent, and therefore the type of the organic solvent is appropriately selected. Is done. When employing a combination of polyvinyl alcohol and ethylene-vinyl alcohol copolymer, it is preferable to use n-butanol. An ethylene-vinyl alcohol copolymer solubilized in a solvent is commercially available, for example, as Soarnol (trade name). The amount of the organic solvent used is usually 30 to 500 parts by weight per 100 parts by weight of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer, acid, and sol-gel method catalyst. .

In the gas barrier laminate film of the present invention, a method for forming a gas barrier coating film will be described below.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier coating solution. In the gas barrier coating liquid, the polycondensation reaction gradually proceeds.

  Next, the gas barrier coating solution is applied by a conventional method on an inorganic oxide vapor-deposited film provided on one surface of the substrate, and dried. By the drying, the polycondensation of the alkoxide, metal alkoxide, silane coupling agent, and vinyl alcohol polymer further proceeds to form a composite polymer layer. Preferably, the above operation is repeated to laminate a plurality of composite polymer layers.

  Finally, the film coated with the coating solution is heated at a temperature of 150 to 250 ° C., preferably 170 to 220 ° C., more preferably 180 to 200 ° C., for 1 second to 2 minutes, preferably 30 to 90 seconds. Thereby, the gas-barrier coating film which has the desired Young's modulus of 15-40 Mpa can be formed on the inorganic oxide vapor deposition film vapor-deposited on the base material. In other words, by controlling the heat treatment temperature and time and setting the Young's modulus of the gas barrier coating film to the above specific one, it has high gas barrier properties and excellent flexibility, and can be made by bag making processing or molding processing. It is possible to obtain a gas barrier laminated film that does not cause damage such as cracks and maintains high gas barrier properties even after the treatment.

  When the heating temperature or time of the film is less than 150 ° C. or less than 1 second, the Young's modulus of the gas barrier coating film is less than 15 MPa, and the gas barrier properties such as the oxygen barrier property and water vapor barrier property of the gas barrier laminate film itself are lowered. At the same time, the gas barrier coating film is damaged due to a molding process or the like, and the gas barrier property is further lowered by the molding process or the like. If the heating temperature or time exceeds 250 ° C. or exceeds 2 minutes, the Young's modulus of the gas barrier coating film exceeds 40 MPa and the flexibility decreases. Damage occurs, and the gas barrier properties after processing such as molding are reduced.

  In this way, by setting the Young's modulus of the gas barrier coating film to the above specific one, the gas barrier multilayer film that maintains a high barrier property even after performing molding processing and other treatments as compared with the conventional one. Can be obtained. The reason for this is considered as follows, but is not limited thereto. That is, by the heat treatment after applying the gas barrier coating solution, a crosslinking reaction occurs in which the vinyl alcohol polymer and the hydrolyzate of alkoxysilane are hydrogen-bonded or chemically bonded inside the coating film, and the vinyl alcohol polymer is crystallized. Furthermore, a hydrogen bond or a chemical bond is formed at the interface between the vapor deposition film and the gas barrier coating film to firmly adhere the vapor deposition film and the gas barrier coating film.

  Therefore, if the heat treatment temperature is too low or the heat treatment time is too short, the above crosslinking reaction, chemical bond or the like is not sufficiently formed, and the Young's modulus does not rise sufficiently. The gas barrier properties are lowered, and the gas barrier coating film is damaged by cracking or the like due to molding or the like, and the gas barrier properties after molding are further lowered. Conversely, if the heat treatment temperature is too high or the heat treatment time is too long, the crosslinking reaction or chemical bond becomes too strong and the flexibility is lowered, that is, the Young's modulus becomes too high. Etc., cracks occur, and the barrier properties after molding process are lowered. Therefore, by controlling the heat treatment temperature and time so as to obtain a desired Young's modulus, the gas barrier property of the gas barrier laminate film itself can be improved, and the gas barrier property does not decrease even after molding. Flexibility can be imparted to the gas barrier laminate film.

  In the present invention, an ethylene / vinyl alcohol copolymer or a composition using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol may be used instead of the vinyl alcohol polymer. A laminated film using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol is further improved in gas barrier properties after hot water treatment such as boil treatment and retort treatment.

  As another aspect of forming the gas barrier coating film, the following laminated film is preferably formed in order to improve the gas barrier property after the hot water treatment.

  That is, a composition containing polyvinyl alcohol is previously formed on at least one surface of a base film to form a first composite polymer layer, and then the ethylene / vinyl alcohol copolymer is contained on the coated surface. The object is applied to further form a second composite polymer layer. Thereby, the gas barrier property of the laminated film obtained improves.

  Furthermore, in the present invention, a plurality of gas barrier coating films may be formed on the substrate film. By providing a plurality of gas barrier coating films, the gas barrier property can be further improved.

  As a method for applying the gas barrier coating film forming composition, for example, a roll coating such as a gravure coater, a spray coating, a spin coating, a dipping, a brush, a barcode, an applicator or the like is applied once or a plurality of times. With this coating, it is possible to form the gas barrier coating film of the present invention having a dry-baked film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm.

  If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance.

  In the embodiment of the present invention, after the vapor deposition layer and the gas barrier coating film are provided on the base material, a vapor deposition layer is further provided, and the gas barrier coating film is formed on the vapor deposition layer in the same manner as described above. Good. Thus, by increasing the number of laminated layers, it is possible to realize a laminated film having further excellent gas barrier properties.

  Since the gas barrier laminate film of the present invention has excellent gas barrier properties and flexibility, it is useful as a packaging material and is particularly suitably used as a food packaging film.

  Furthermore, the gas barrier laminate film of the present invention is excellent in gas barrier properties after hot water treatment, particularly after high pressure hot water treatment (retort treatment).

Packaging laminate now as a packaging bag using the present gas barrier laminate film, on a gas barrier coating film of the gas barrier laminate film as an example, the printing layer, laminating the adhesive layer, were sequentially provided a heat sealable resin layer The laminated material for packaging materials will be described.

Print layer The print layer is composed of one or more ordinary ink vehicles as a main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, and a curing agent. Add one or more additives such as crosslinking agents, lubricants, antistatic agents, fillers, etc., and add colorants such as dyes and pigments, and use solvents, diluents, etc. Kneading to prepare an ink composition, then using the ink composition, for example, using a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, gas barrier lamination On the gas barrier coating film of the film, a desired printed pattern composed of characters, figures, symbols, patterns and the like can be printed to form a printed pattern layer.

  In the above, as the ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, Sierrac, alkyd resin, phenolic resin, maleic acid resin, Natural resins, hydrocarbon resins, polyvinyl chloride resins, polyvinyl acetate resins, polystyrene resins, polyvinyl propylar resins, acrylic or methacrylic resins, polyamide resins, polyester resins, polyurethane resins, epoxy resins, One or more of urea resin, melamine resin, aminoalkyd resin, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber and the like can be used.

Laminate adhesive layer Next, the laminate adhesive layer constituting the laminate will be described. Examples of the adhesive constituting the adhesive layer for laminating include, for example, polyvinyl acetate adhesive, homopolymers such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl ester, and these and methyl methacrylate, acrylonitrile, and styrene. Polyacrylic acid ester adhesives, cyanoacrylate adhesives, and copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, and methacrylic acid. Polymer-based adhesives, cellulose-based adhesives, polyester-based adhesives, polyamide-based adhesives, polyimide-based adhesives, amino resin-based adhesives such as urea resins or melamine resins, phenolic resin-based adhesives, epoxy-based adhesives, Polyurethane adhesives, reactive (meth) acrylic adhesives, Ropurengomu, nitrile rubber, styrene - rubber adhesive consisting of such butadiene rubber, silicone adhesive, an alkali metal silicate, may be used adhesives inorganic adhesive or the like made of a low-melting-point glass or the like.

  The above-mentioned adhesive may be in any form of composition such as aqueous type, solution type, emulsion type, and dispersion type, and the property may be any form such as film / sheet, powder or solid. Further, the adhesion mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.

In the present invention, the adhesive is applied to the entire surface including the printing layer by, for example, a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or a printing method, and then the solvent is dried. Thus, an adhesive layer for laminating can be formed, and the coating or coating amount is preferably 0.1 to 10 g / m ² (dry state).

Heat-sealable resin layer Next, the heat-sealable resin layer will be described. The heat-sealable resin constituting the heat-sealable resin layer may be any resin that can be melted by heat and mutually melted. For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (line ) Low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polyethylene and polypropylene, or acid-modified polyolefin resins obtained by modifying these resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid Seed or more resin film or sea It can be used.

  In the present invention, the heat-sealable resin layer can be formed by dry laminating the above-described resin film or sheet on the surface of the laminating adhesive layer.

  The resin film or sheet can be used in a single layer or multilayer, and the thickness of the resin film or sheet is 5 to 300 μm, preferably 10 to 110 μm.

  The thickness of the resin film or sheet described above is such that scratches and cracks are formed on the inorganic oxide vapor deposition film constituting the resin film or sheet having the inorganic oxide vapor deposition film when the bag-shaped container body is made. In order to prevent the occurrence of the above, it is preferable to relatively increase the film thickness, specifically, 70 to 110 μm, preferably 80 to 100 μm.

  In the present invention, it is particularly preferable to use linear low-density polyethylene among the above-described resin films or sheets. Linear low-density polyethylene has the advantage of improving impact resistance with less propagation of breakage due to its stickiness, and because the inner layer is always in contact with the contents, it is resistant to environmental stress. It is also effective to prevent cracking deterioration.

  Further, in the present invention, other resins can be blended with the linear low density polyethylene. For example, by blending an ethylene-ptyne copolymer or the like, it is slightly inferior in heat resistance and sealed in a high temperature environment. Although the stability tends to deteriorate, there is an advantage that the tearability is improved and it contributes to easy opening.

  As the linear low-density polyethylene, specifically, an ethylene-α-olefin copolymer film or sheet polymerized using a metallocene catalyst can be used in the same manner. Examples of the ethylene-α-olefin copolymer film or sheet polymerized using the above metallocene catalyst include, for example, a catalyst based on a combination of a metallocene complex and an alumoxane, such as a catalyst based on a combination of zirconocene dichloride and methylalumoxane. An ethylene-α-olefin copolymer film or sheet obtained by polymerization using a metallocene catalyst can be used.

The metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Epolyu” manufactured by Mitsui Petrochemical Industry Co., Ltd., and the product name “EXACT” manufactured by Exxon Chemical Company, USA ”, A film of an ethylene-α-olefin copolymer polymerized using a metallocene catalyst such as“ Affinity ”or“ Engage ”manufactured by Dow Chemical Co., USA. Can do.

  The film or sheet constituting the heat-sealable resin layer can be used as a single layer or multiple layers, and the thickness thereof is 5 to 300 μm, preferably 10 to 100 μm.

  In the present invention, when a film or sheet of an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is used as the resin film having heat sealability as described above, when manufacturing a bag body Furthermore, it has the advantage that low temperature heat sealability is possible.

  In the present invention, a resin film (intermediate base material) may be sandwiched between the laminating adhesive layer and the heat-sealable resin layer. By providing such an intermediate layer, strength, puncture resistance, and the like are improved. As a resin film, it has excellent strength in mechanical, physical, chemical, etc., excellent in puncture resistance, etc. In addition, it is excellent in heat resistance, moisture resistance, pinhole resistance, transparency, etc. Any film or sheet can be used.

  Specifically, for example, polyester resins, polyamide resins, polyaramid resins, polypropylene resins, polycarbonate resins, polyacetal resins, fluorine resins, and other tough resin films or sheets can be used.

  In the present invention, the above-described resin film or sheet is used. For example, the above-described laminating adhesive or the like is used for dry lamination or the like, and the laminating adhesive layer and the heat-sealable resin are used. Can be sandwiched between layers.

As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, and the like, and if it is too thick, the cost increases. On the other hand, if it is too thin, the strength, puncture resistance and the like are reduced, which is not preferable.
In the present invention, about 10 to 100 μm, preferably 12 to 50 μm is preferable for the reasons described above.

  Usually, packaging bags are subjected to severe physical and chemical conditions, so the laminated material constituting the packaging bags is required to have strict packaging suitability, deformation prevention strength, drop impact strength, Various conditions such as pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, and hygiene are required. For this reason, in the present invention, in addition to the above materials, other materials satisfying the above various conditions can be arbitrarily used. Specifically, for example, low density polyethylene, Medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid Copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile Resin, polystyrene resin, acrylonitrile-styrene copolymer (A Resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, A film or sheet of a known resin such as a gen-based resin, a polyacetal-based resin, a polyurethane-based resin, or nitrocellulose can be arbitrarily selected and used. In addition, for example, synthetic paper or the like can also be used.

In the present invention, the film or sheet may be any of unstretched, uniaxially or biaxially stretched. Moreover, although the thickness is arbitrary, it can select and use from the range of several micrometers-300 micrometers.
Furthermore, in the present invention, the film or sheet may be any form of film such as extrusion film formation, inflation film formation, and coating film.

  As described above, the present invention provides a gas barrier property in which a vapor deposition film of an inorganic oxide is provided on one surface of a base film, and then a gas barrier coating film is provided on the vapor deposition film of the inorganic oxide. On the gas barrier coating film of the laminate, a printing pattern layer and a laminating adhesive layer are sequentially provided by using various coating methods, printing methods, dry laminating methods, and the like. A heat-sealable resin layer is provided on the adhesive layer, and the resin film has strength and excellent puncture resistance between the adhesive layer for lamination and the heat-sealable resin layer. By laminating (intermediate base material), a laminated material for a packaging bag can be produced.

Packaging Bag A packaging bag using the above laminated material will be described. The bag-shaped container body made of a wearing bag uses the above-mentioned laminated material made of a gas barrier laminated film, folds the laminated material into two, and overlaps the surfaces of the heat-sealable resin layers facing each other. The package can be manufactured by heat-sealing the part to form a cylindrical package, then sealing the bottom, filling the contents, and sealing the top.

  As the bag making method, the laminated material as described above is folded or overlapped so that the inner layer faces each other, and the peripheral end thereof is, for example, a side seal type, a two-side seal type, a three-side seal. Various types of heat seals such as molds, four-sided seals, envelope stickers, pillow seals, pleated seals, flat bottom seals, square bottom seals, gussets, etc. A form of wearing bag can be produced. In addition, for example, a self-supporting packaging bag (standing pouch) is also possible.

  In the above, the heat sealing method can be performed by a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, and the like.

  Although the present invention will be described more specifically with reference to examples, the present invention is not limited to these examples.

[Example 1]
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as a base film, and first, the above biaxially stretched polyethylene terephthalate film was mounted on a feed roll of a take-up vacuum deposition apparatus. Next, this was fed out, and the following corona discharge treatment surface of the biaxially stretched polyethylene terephthalate film was subjected to the following vacuum deposition method using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source. An aluminum oxide vapor deposition film having a thickness of 200 mm was formed according to the vapor deposition conditions.
(Deposition conditions)
Degree of vacuum in vapor deposition chamber after introduction of oxygen gas: 2 × 10 ⁻⁴ mbar
Degree of vacuum in the winding chamber: 2 × 10 ^-2 mbar
Electron beam power: 25kW
Film transport speed: 240 m / min Deposition surface: Corona discharge treatment surface

Then, a glow discharge plasma generator is used on the vapor deposition film surface of aluminum oxide, and a mixed gas consisting of power 9 kw, oxygen gas: argon gas = 7.0: 2.5 (unit: slm) is used, and the mixed gas Oxygen / argon mixed gas plasma treatment was performed at a pressure of 6 × 10 ⁻² mbar and a treatment speed of 420 m / min to form a plasma treated surface in which the surface tension of the deposited film surface of aluminum oxide was improved by 54 dyne / cm or more.

(2) On the other hand, according to the composition shown in Table 1, composition a. Hydrolyzed liquid consisting of orthoethyl silicate (manufactured by Tama Kagaku), isopropyl alcohol, 0.5 N hydrochloric acid aqueous solution, ion-exchanged water, silane coupling agent, A polyvinyl alcohol aqueous solution having a composition b. Prepared in advance was added and stirred to obtain a colorless and transparent gas barrier coating solution.
(Table 1) Barrier coating solution composition:
a Normal ethyl silicate (manufactured by Tama Science Co., Ltd.)
Isopropyl alcohol 3.90
0.5N hydrochloric acid aqueous solution 0.50
H ₂ O 21.80
Silane coupling agent 1.60
(Γ-glycidoxypropyltrimethoxysilane)
b Polyvinyl alcohol 2.30
(RS-110: manufactured by Kuraray Co., Ltd., degree of saponification = 99%, degree of polymerization = 1,000)
Isopropyl alcohol 2.700
H ₂ O 51.20
Total 100.000 (wt%)

Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier coating solution produced above by a gravure roll coating method, and then heated at 150 ° C. for 60 seconds to obtain a thickness. A gas barrier coating film of 0.2 μm (dry operation state) was formed to produce a gas barrier laminated film of the present invention.

[Example 2]
A gas barrier laminate film of the present invention was produced in the same manner as in Example 1 except that the heat treatment after coating the gas barrier composition was performed at 180 ° C.

[Example 3]
A gas barrier laminate film of the present invention was produced in the same manner as in Example 1 except that the heat treatment after coating the gas barrier composition was performed at 200 ° C.

[Example 4]
A biaxially stretched polyester film having a thickness of 12 μm was used, and this was mounted on a feeding roll of a plasma chemical vapor deposition apparatus, and the thickness of the biaxially stretched polyester film on the corona discharge-treated surface was as follows. A 200-nm silicon oxide vapor deposition film was formed.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film ^- forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power: 35kW

After that, a glow discharge plasma generator is used on the vapor deposition film surface of silicon oxide, a mixed gas consisting of power 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: slm) is used, and the mixed gas Oxygen / argon mixed gas plasma treatment was performed at a pressure of 6 × 10 ⁻² mbar and a treatment speed of 420 m / min to form a plasma treated surface in which the surface tension of the deposited silicon oxide film surface was improved by 54 dyne / cm or more.

  Next, a gas barrier coating film was formed on the deposited silicon oxide film in the same manner as in (2) of Example 1 except that the heat treatment after coating the gas barrier composition was performed at 200 ° C. The gas barrier laminate film of the present invention was produced.

[Comparative Example 1]
A gas barrier laminate film was produced in the same manner as in Example 1 except that the heat treatment after coating the gas barrier composition was performed at 100 ° C. for 30 seconds.

[Comparative Example 2]
A gas barrier laminate film was produced in the same manner as in Example 1 except that the heat treatment after coating the gas barrier composition was performed at 120 ° C. for 60 seconds.

[Comparative Example 3]
A gas barrier laminated film was produced in the same manner as in Example 1 except that the heat treatment after coating the gas barrier composition was performed at 250 ° C. for 3 minutes.

[Experimental example]
1. Calculation of Young's modulus of gas barrier coating film (1) Measurement of displacement amount The biaxially stretched polyethylene terephthalate film (thickness 12 μm) of Example 1 is cut into a strip shape having a width of 2 mm and a length of 25 mm, and one end in the longitudinal direction thereof is cut. The height difference (displacement amount) from the opposite free end was measured at 25 ° C. Furthermore, the displacement amount of the biaxially stretched polyethylene terephthalate film in which the aluminum oxide vapor-deposited film was formed under the same conditions as above and the gas barrier laminate films of Examples 1 to 4 and Comparative Examples 1 to 3 were measured. The results are shown in Table 2 below.

(2) Measurement of layer density The layer density of the biaxially stretched polyethylene terephthalate film, the aluminum oxide vapor deposition film, and the gas barrier coating film was calculated from the volume and weight. The results are shown below.
Biaxially stretched polyethylene terephthalate film: 1.4 g / cm ³
Aluminum oxide vapor deposition film: 3 g / cm ³
Gas barrier coating films (Examples 1 to 4, Comparative Examples 1 to 3): 1.5 g / cm ³

(3) Calculation of Young's modulus of gas barrier coating film (a) Calculation of Young's modulus of biaxially stretched polyethylene terephthalate film Displacement amount of biaxially stretched polyethylene terephthalate film measured in (1) above, layer density, etc. It was 6.2 GPa when the Young's modulus of the biaxially stretched polyethylene terephthalate film was calculated using the following mathematical formula.
_{X 1 = {- b × (} h 1 × d 1/2) × 3L 4/12} / (E × Iy)
_{E × Iy = E 1 × bh} 1 3/12
α ₁ = h _1/2
(Where X ₁ is the amount of displacement of the biaxially stretched polyethylene terephthalate film, E and E ₁ are the Young's modulus of the biaxially stretched polyethylene terephthalate film, and b, L and h ₁ are the width, length and thickness of the film, respectively. D ₁ represents the density of the film, Iy ₁ represents the moment of inertia of bending of the film, and α ₁ represents the neutral plane of the moment of the film.)

(B) Calculation of Young's modulus of aluminum oxide vapor deposition film Displacement amount of the biaxially stretched polyethylene terephthalate film formed with the aluminum oxide vapor deposition film measured in the above (1) and (2), layer density of the aluminum oxide vapor deposition film, and the above Using the Young's modulus of the biaxially stretched polyethylene terephthalate film calculated in (a) and the following mathematical formula, the Young's modulus of the aluminum oxide deposited film was calculated to be 285.9 GPa.
_{X 2 = [- b × {} (h 1 × d 1/2) + (h 2 × d 2/2)} × 3L 4/12] / (E × Iy)
E × Iy = (b / 3) × {E ₁ × (h ₁ -α ₂ ) ³ + E ₁ × (-α ₂ ) ³ + E ₂ (h ₁ + h ₂ -α ₂ ) ³ -E ₂ ( h ₁ -α ₂ ) ³ }
α ₂ = {E ₁ h ₁ ² + E ₂ h ₂ (2h ₁ + h ₂ )} / {2E ₁ h ₁ + 2E ₂ h ₂ }
(Where X ₂ is the amount of displacement of the biaxially stretched polyethylene terephthalate film on which the aluminum oxide vapor deposition film is formed, b and L are the width and length of the film, E is the Young's modulus of the film, and Iy is the thickness of the film, respectively. The moment of inertia of bending, α ₂ is the neutral plane of the moment of the film, E ₂ is the Young's modulus of the aluminum oxide deposited film, h ₂ is the thickness of the deposited film, d ₂ is the density of the deposited film, and Iy ₂ is Represents the moment of inertia of bending of the deposited film, and E ₁ , h ₁ , d ₁ , and Iy ₁ are as described above.)

(C) Calculation of Young's modulus of gas barrier coating film Displacement amount of gas barrier laminated film measured in (1) and (2) above, layer density of gas barrier coating film, and calculation in (a) and (b) above Using the Young's modulus of the biaxially stretched polyethylene terephthalate film or the like and the following formula, the Young's modulus of the gas barrier coating film was calculated to be 18.8 MPa.
_{X 3 = [- b × {} (h 1 × d 1/2) + (h 2 × d 2/2) + (h 3 × d 3/2)} × 3L 4/12] / (E × Iy)
E × Iy = (b / 3) × (E ₁ × (h ₁ -α ₃ ) ³ + E ₁ × (-α ₃ ) ³ + E ₂ × (h ₁ + h ₂ -α ₃ ) ³ -E ₂ × (h ₁ -α ₃ ) ³ + E ₃ × (h ₁ + h ₂ + h ₃ -α ₃ ) ³ -E ₃ × (h ₁ + h ₂ -α ₃ ) ³ }
α ₃ = {E ₁ h ₁ ² + E ₂ h ₂ (2h ₁ + h ₂ ) + E ₃ h ₃ (2h ₁ + 2h ₂ + h ₃ )} / {2E ₁ h ₁ + 2E ₂ h ₂ + 2E ₃ h ₃ }
(Where X ₃ is the amount of displacement of the gas barrier laminate film, b and L are the width and length of the film, E is the Young's modulus of the film, Iy is the moment of inertia of bending of the film, and α ₃ is the above neutral plane of the moments of the film, E ₃ is the Young's modulus of the gas barrier coating film, h ₃ is the thickness of the coating film, the density of d ₃ the coating film, Iy ₃ is the moment of inertia of bending of the coating film E ₁ , E ₂ , h ₁ , h ₂ , d ₁ , d ₂ , Iy ₁ , Iy ₂ are as described above.)

The Young's modulus of the gas barrier coating films of Examples 2 to 4 and Comparative Examples 1 to 3 was calculated in the same manner as in the above (1) to (3). The results are shown in Table 3 below.

2. Measurement of Oxygen Permeability The gas barrier laminate films produced in Examples 1 to 4 and Comparative Examples 1 to 3 were bonded to a sealant film, and a four-side seal pouch was produced with a bag making machine. Furthermore, in order to evaluate the hot water resistance of each gas barrier laminate film, the four-sided seal pouch prepared as described above was boiled (retorted) at 120 ° C. for 30 minutes in a high-pressure kettle.
Next, the gas barrier laminated films produced in Examples 1 to 4 and Comparative Examples 1 to 3, each four-side seal pouch prepared as described above, and each four-side seal pouch after retorting, a temperature of 23 ° C. and a humidity of 90 In accordance with JIS standard K7126, using a measuring machine [model name, OXTRAN] manufactured by MOCON, USA under the condition of% RH
The oxygen permeability was measured.
The results are shown in Tables 4 to 6 below.

3. Measurement of water vapor permeability Gas barrier laminate films produced in Examples 1 to 4 and Comparative Examples 1 to 3, each four-sided seal pouch created in the above "2. Measurement of oxygen permeability", and each four-side after retorting For seal pouches, using a measuring machine manufactured by MOCON (model name, PERMATRAN) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, JIS standard
The water vapor permeability was measured according to K7129.
The results are shown in Tables 4 to 6 below.

"Measurement result"
As shown in Tables 4 to 6 above, the gas barrier laminate films of Examples 1 to 4 are superior in gas barrier properties of the gas barrier laminate films themselves as compared to Comparative Examples 1 to 3, and after bag making, The gas barrier property after retort treatment was remarkably excellent.
For example, the gas barrier coating film of Example 3 was formed by performing a heat treatment at 200 ° C. for 60 seconds after applying the gas barrier coating solution, and had a Young's modulus of 21.5 MPa. The oxygen permeability and water vapor permeability of the gas barrier laminate film of Example 3 were 0.1 cc / m ² · day and 0.1 g / m ² · day, respectively, and it was confirmed that the gas barrier laminate film had high gas barrier properties. And even after bag making on a four-sided seal pouch, the oxygen permeability and water vapor permeability hardly changed to 0.2 cc / m ² · day and 0.3 g / m ² · day, respectively, and even after retorting, No significant changes were observed, 1.1 cc / m ² · day and 1.8 g / m ² · day, respectively.

On the other hand, the gas barrier coating film of Comparative Example 1 was formed by performing heat treatment at a low temperature of 100 ° C. for 30 seconds after applying the gas barrier coating liquid. In comparison, it had a low Young's modulus. The oxygen permeability and water vapor permeability of the gas barrier laminate film of Comparative Example 1 are 0.9 cc / m ² · day and 1.8 g / m ² · day, respectively, which are inferior to those of Examples. there were. Furthermore, after bag-making on a four-sided seal pouch, the oxygen permeability and water vapor permeability are 1.5 cc / m ² · day, 2.2 g / m ² · day, respectively, and the oxygen permeability and water vapor permeability after retorting are These values were 2.2 cc / m ² · day and 3.0 g / m ² · day, respectively, and these values were greatly increased as compared with Examples. That is, it was confirmed that the gas barrier property laminated film of Comparative Example 1 was significantly deteriorated in gas barrier property as compared with the Examples by bag making and retort treatment.

In addition, the gas barrier coating film of Comparative Example 3 was formed by performing a heat treatment at 250 ° C. for 2 minutes after applying the gas barrier coating liquid, but it was 42.9 MPa, compared with the example. It had a high Young's modulus. The oxygen permeability and water vapor permeability of the gas barrier laminate film of Comparative Example 3 are 0.1 cc / m ² · day and 0.7 g / m ² · day, respectively, which are inferior to those of the examples. there were. Further, the oxygen permeability and water vapor permeability after bag making in the four-side sealed pouch of Comparative Example 3 were 3.0 cc / m ² · day, 3.5 g / m ² · day, respectively, oxygen permeability after retorting, water vapor The transmittances were 3.6 cc / m ² · day and 4.5 g / m ² · day, respectively, and these values were greatly increased as compared with Examples. That is, it was confirmed that the gas barrier property laminated film of Comparative Example 3 was significantly deteriorated in gas barrier properties as compared with the Examples by bag making or retort treatment.
As described above, by controlling the heat treatment temperature and time after application of the gas barrier coating liquid and by making the Young's modulus of the gas barrier coating film specific, it has high gas barrier properties and excellent flexibility, It was confirmed that a gas barrier laminate film that maintains high gas barrier properties can be obtained even after bag making, molding, filling, and sterilization treatment steps.

It is the schematic cross section which showed an example of the layer structure of the gas barrier laminated film of this invention. It is the schematic cross section which showed the other example of the layer structure of the gas barrier laminated film of this invention. It is the schematic of the chemical vapor deposition apparatus used for the method of this invention. It is the schematic of the chemical vapor deposition apparatus used for the method of the other aspect of this invention. It is the schematic of the physical vapor deposition apparatus used for the method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 1a Processed surface 1b Primer coat layer 2 Deposition film 3 Gas barrier coating film 21 Plasma chemical vapor deposition apparatus 22 Vacuum chamber 23 Unwinding roll 24 Auxiliary roll 25 Cooling / electrode drum 26, 27 Gas supply apparatus 28 Raw material volatilization Supply device 29 Raw material supply nozzle 30 Glow discharge plasma 31 Power source 32 Magnet 33 Guide roll 34 Winding roll 35 Vacuum pump 40 Plasma chemical vapor deposition apparatus 41 Base film supply chamber 42 First film formation chamber 43 Second film formation Chamber 44 Third film forming chamber 45 Winding chamber 46 Unwinding roll 47 Auxiliary roll 48 Cooling / electrode drum 49 Raw material volatilization supply device 50 Gas supply device 51 Raw material supply nozzle 52 Glow discharge plasma 53, 54 Auxiliary roll 55 Cooling / electrode Drum 56 Raw material volatilization Device 57 Gas supply device 58 Material supply nozzle 59 Glow discharge plasma 60, 61 Auxiliary roll 62 Cooling / electrode drum 63 Material volatilization supply device 64 Gas supply device 65 Material supply nozzle 66 Glow discharge plasma 67 Auxiliary roll 68 Winding roll 69 Power supply 70 , 71, 72 Magnet 80 Winding type vacuum deposition apparatus 81 Winding chamber 82 Unwinding roll 83, 84 Guide roll 85 Coating drum 86 Deposition source 87 Oxygen gas outlet 88 Mask 89, 90 Guide roll 91 Winding roll 92 Crucible 93 Deposition chamber

Claims (17)

A gas barrier laminate film in which a vapor deposition film of an inorganic oxide is provided on a substrate, and a gas barrier coating film is provided on the vapor deposition film,
A gas barrier laminate film, wherein the gas barrier coating film has a Young's modulus of 15 to 40 MPa.   The gas barrier laminate film according to claim 1, wherein the base material is a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film.   The gas barrier laminate film according to claim 1 or 2, wherein a pretreatment is performed on the surface side of the base material on which the inorganic oxide vapor deposition film is provided prior to the formation of the vapor deposition film. A gas barrier laminate film, characterized by discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, or oxidation treatment using chemicals.   The gas barrier laminate film according to any one of claims 1 to 3, wherein a primer coating treatment is performed on the surface side of the substrate on which the inorganic oxide vapor deposition film is provided prior to the formation of the vapor deposition film. A gas barrier laminate film, wherein the primer coat treatment is performed by applying a coating liquid comprising polyester, acrylic, urethane resin, and isocyanate curing agent on a substrate.   The gas barrier laminate film according to any one of claims 1 to 4, wherein the vapor-deposited film is post-treated, and the post-treatment is glow discharge treatment, plasma treatment, or microwave treatment. A gas barrier laminate film characterized by The gas barrier coating film has the general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal atom, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and n is 0 or more) Wherein m is an integer of 1 or more, and n + m represents the valence of M), and a composition comprising at least one alkoxide, polyvinyl alcohol, and / or ethylene / vinyl alcohol The gas barrier laminate film according to any one of claims 1 to 5, which is a hydrolyzate of alkoxide obtained by polycondensation by a sol-gel method or a hydrolyzed condensate of alkoxide.   The gas barrier laminate film according to claim 6, wherein the composition further comprises a silane coupling agent. It is a manufacturing method of the gas-barrier laminated film as described in any one of Claims 1-7, Comprising: The vapor deposition film | membrane of an inorganic oxide is formed on a base material,
A manufacturing method characterized by forming a gas barrier coating film by applying a gas barrier coating liquid on the deposited film and heating at 150 to 250 ° C. for 1 second to 2 minutes.   The manufacturing method according to claim 8, wherein a pretreatment is further performed on the surface of the substrate on which the inorganic oxide vapor deposition film is provided prior to the formation of the vapor deposition film, wherein the pretreatment includes corona discharge treatment and ozone treatment. And a low-temperature plasma treatment using oxygen gas or nitrogen gas, a glow discharge treatment, or an oxidation treatment using a chemical.   The manufacturing method according to claim 8 or 9, wherein a primer coat treatment is further performed on the surface side of the base material on which the inorganic oxide vapor deposition film is provided, prior to the formation of the vapor deposition film. A manufacturing method comprising applying a coating liquid comprising acrylic, urethane resin, and isocyanate curing agent on a substrate.   The manufacturing method according to any one of claims 8 to 10, wherein the vapor deposition film is further subjected to post-treatment, wherein the post-treatment is glow discharge treatment, plasma treatment, or microwave treatment. Manufacturing method.   The said heating temperature is 170-220 degreeC, The manufacturing method as described in any one of Claims 8-11 characterized by the above-mentioned.   A packaging laminate using the gas barrier laminate film according to claim 1, wherein a heat sealable resin layer is provided on the gas barrier coating film of the laminate film.   14. The packaging laminate according to claim 13, wherein a printed layer, a laminate adhesive layer, and a heat sealable resin layer are provided on the gas barrier coating film.   The packaging laminate according to claim 13 or 14, wherein the heat-sealable resin layer is a polyolefin-based resin.   The packaging laminate according to any one of claims 13 to 15, wherein an intermediate substrate is provided between the gas barrier coating film and the heat-sealable resin layer. It is a packaging bag using the packaging laminated material as described in any one of Claims 13-16, Comprising: The heat sealable resin layer side of one packaging laminated material, and the heat sealing of the other packaging laminated material A packaging bag characterized in that it is overlapped with the conductive resin layer side and heat-sealed at its end.

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