JP2008264998A - Gas barrier laminated film, its manufacturing method, packaging laminated material using gas barrier laminated film and packaging bag - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier laminated film having high gas barrier properties and excellent in the storage properties of contents, and to provide its manufacturing method. <P>SOLUTION: The gas barrier laminated film is constituted by providing a vapor deposition film 2 of an inorganic oxide on a base material 1 and providing a gas barrier coating film 3 on the vapor deposition film. The gas barrier coating film comprises an alkoxide hydrolysate or alkoxide hydrolyzed condensate obtained by the polycondensation of a composition containing at least a kind of an alkoxide represented by the general formula. R<SP>1</SP><SB>n</SB>M(OR<SP>2</SP>)<SB>m</SB>(wherein M is a metal element, R<SP>1</SP>and R<SP>2</SP>are each a 1-8C organic group, n is an integer of 0 or above, m is an integer of 1 or above and n+m is a valence of M), polyvinyl alcohol and/or ethylene/vinyl alcohol by a sol-gel method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a laminated film having gas barrier properties, a production method thereof, a laminated material for packaging using the same, and a packaging bag. More specifically, a gas barrier laminate film that has a superior gas barrier property that highly inhibits permeation of water vapor and the like, and is useful for manufacturing various packaging containers, its manufacturing method, and packaging using the same The present invention relates to a laminated material and a packaging bag.

  Packaging materials for filling and packaging foods, beverages, chemicals, miscellaneous goods, etc. must have a gas barrier property that blocks and prevents the permeation of oxygen gas, water vapor, etc., in order to prevent alteration and discoloration of the contents to be filled and packaged. Required.

Conventionally, as a packaging material having gas barrier properties, a packaging material in which an aluminum foil layer is provided on a base material has been 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 is provided, there is a problem that a packaging material having transparency cannot 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, and has no environmental problems at the time of disposal.

  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.

  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 by comprising:

Patent Document 1 discloses laminating a gas barrier coating on the vapor deposition layer, but does not define any alkoxide amount with respect to the water-soluble polymer. As a result, the gas barrier laminate film described in Patent Document 1 has a problem that it is poor in gas barrier properties such as water vapor.
Japanese Patent No. 2790054

  As described above, the gas barrier laminate film is required to have high gas barrier properties, but a gas barrier laminate film having such properties has not been obtained.

  On the other hand, the present invention has a gas barrier laminate film having a higher gas barrier property that prevents permeation of water vapor and the like, and excellent storage stability of contents, a method for producing the same, as compared with conventional ones, The laminated material used for packaging and the packaging bag are provided.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a gas barrier laminated film in which an inorganic oxide is vapor-deposited on a substrate and a gas barrier coating film is formed thereon, is contained in the gas barrier coating film. Depending on the content ratio of the alkoxide to be formed and the water-soluble polymer, the center line surface roughness (hereinafter referred to as “surface roughness (Ra)”) of the gas barrier coating film surface changes, and the surface roughness It has been found that gas barrier properties such as water vapor are particularly lowered when the thickness (Ra) is increased, and gas barrier properties are improved when the surface roughness (Ra) is reduced. As a result of further research, the change in the surface roughness (Ra) is caused by an element between an alkoxide-derived metal element (M) and a carbon element (C) derived from a water-soluble polymer contained in the gas barrier coating film. It depends on the ratio, and by making these element ratios predetermined, the surface roughness (Ra) can be reduced compared to the conventional one, and as a result, the gas barrier property is extremely high. The present inventors have found that a gas barrier laminate film having the above can be obtained and completed the present invention.

That is, this invention includes the invention shown to the following (a)-(c).
(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,
The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal element, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and n is 0 or more) A composition comprising at least one alkoxide, polyvinyl alcohol and / or ethylene / vinyl alcohol represented by: m is an integer of 1 or more, and n + m represents a valence of M). , An alkoxide hydrolyzate obtained by polycondensation by a sol-gel method, or a gas barrier coating film by an alkoxide hydrolysis condensate,
Here, the element ratio (Atomic%) of the metal element (M) derived from the alkoxide and the carbon element (C) derived from polyvinyl alcohol and / or ethylene / vinyl alcohol in the gas barrier coating film,
2.8 <M / C <4.12
The gas barrier laminate film as described above.

(B) The surface roughness (Ra) of the gas barrier coating film is
0.15 (nm) <Ra <0.275 (nm)
The gas barrier laminate film according to (a), wherein

(C) A method for producing a gas barrier laminate film of (a) or (b),
Form a vapor-deposited film of inorganic oxide on the substrate,
On the vapor-deposited film, a general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal element, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and n is 0 or more. A composition comprising at least one alkoxide, polyvinyl alcohol, and / or ethylene / vinyl alcohol represented by: an integer, m is an integer of 1 or more, and n + m represents a valence of M). , An alkoxide hydrolyzate obtained by polycondensation by a sol-gel method, or a gas barrier coating film by an alkoxide hydrolysis condensate, and an element of a metal element (M) and a carbon element (C) in the gas barrier coating film Percentage (Atomic%)
2.8 <M / C <4.12
A method for producing a gas barrier laminate film comprising: forming a gas barrier coating film.

  The gas barrier coating film in the gas barrier laminate film of the present invention comprises a three-dimensional network composite polymer layer formed by a polycondensation reaction between alkoxides or alkoxide and a water-soluble polymer such as polyvinyl alcohol. By making the element ratio of the metal element derived from the alkoxide and the carbon element derived from the water-soluble polymer contained in the gas barrier coating film specific, a denser and stronger three-dimensional network composite A polymer layer is formed, and the surface roughness (Ra) of the gas barrier coating film surface decreases. As a result, the gas barrier laminate has excellent transparency, impact resistance, hot water resistance, etc., while stably maintaining extremely high gas barrier properties, particularly with respect to water vapor, etc. A film can be obtained.

  Further, as described above, since the gas barrier laminate film of the present invention has a small surface roughness (Ra), when bonded to another intermediate layer or a heat-sealable resin layer, the gas barrier coating film and the other A packaging material having high adhesion with the intermediate layer can be obtained. That is, when the gas barrier film of the present invention is used, it is possible to produce a packaging laminate and a packaging bag having higher physical strength than the conventional one.

  In the present invention, when an inorganic oxide vapor-deposited film is formed on the substrate by chemical vapor deposition, the inorganic oxide oxidizes the plasma source gas with oxygen gas on the substrate. However, since it is formed in the form of a thin film in the form of an oxide, the formed vapor-deposited film of the inorganic oxide is a dense, flexible continuous layer with few gaps. Accordingly, 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 a conventional vacuum vapor deposition method or the like. Can provide sufficient gas barrier properties.

  Furthermore, in the present invention, when an inorganic oxide vapor deposition film is formed on a substrate by chemical vapor deposition, the content of the inorganic oxide is decreased from the surface of the vapor deposition film in the depth direction. This makes it possible to improve impact resistance and the like. On the other hand, since the content of the inorganic oxide is small at the interface with the base material, the tight adhesion between the base material and the deposited film of the inorganic oxide is strong. Therefore, a gas barrier laminate film having a higher gas barrier property can be obtained.

The gas barrier laminate film of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view 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 is provided with an inorganic oxide vapor deposition film 2 on one surface of a base film 1, and further, on the inorganic oxide vapor deposition film 2, a gas barrier is provided. The structure provided with the conductive coating film 3 is a basic structure.

  As another embodiment of the gas barrier laminate film of the present invention, as shown in FIG. 2, a primer coat layer 1a is provided on one surface of a substrate film 1, and an inorganic oxide vapor deposition film 2 is provided on the primer coat layer. Further, a gas barrier coating film 3 may be provided on the inorganic oxide vapor deposition film 2.

  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 shown, in order to improve the adhesion between the base material film and the inorganic oxide deposition film, the surface of the base material is subjected to corona discharge treatment, ozone treatment, low temperature plasma treatment, or glow treatment before the inorganic oxide deposition. A treatment such as an electric discharge treatment may be applied, or a primer, that is, a coating liquid composed of polyester, acrylic, urethane resin, and isocyanate curing agent may be applied to the surface of the substrate. Furthermore, in the above 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 or different types.

  In the gas barrier laminate film of the present invention, the gas barrier coating film contains an alkoxide and a water-soluble polymer. The element ratio (M / C) of the metal element (M) derived from the alkoxide and the carbon element (C) derived from the water-soluble polymer must be 2.8 <M / C <4.12. Preferably, it is desirable that 2.8 <M / C <3.4. If the amount of carbon element derived from the water-soluble polymer is too large, the swelling of the water-soluble polymer cannot be suppressed, the surface roughness (Ra) increases, and the gas barrier property decreases. If the amount of the metal element derived from the alkoxide is too large, the crosslinking reaction between the alkoxides or between the alkoxide and the water-soluble polymer proceeds excessively, a large aggregate is formed, and a dense film cannot be formed. As a result, the surface roughness (Ra) increases, and the gas barrier property decreases.

  That is, in the present invention, the element ratio (M / C) between the metal element (M) derived from the alkoxide and the carbon element (C) derived from the water-soluble polymer in the gas barrier coating film is specified. By comparison, the surface roughness (Ra) is 0.15 (nm) <Ra <0.275 (nm), preferably 0.175 (nm) <Ra <0.25 (nm) compared with the conventional one. Thus, a gas barrier laminate film having a small surface roughness (Ra) can be obtained. As a result, a gas barrier laminate film having a very high gas barrier property can be obtained, and when this is used as a material constituting a packaging material, adhesion between the gas barrier coating film and another intermediate layer is achieved. A highly packaging material can be obtained.

In addition, the element ratio of the metal element (M) derived from the alkoxide and the carbon element (C) derived from the water-soluble polymer referred to in the present invention is an X-ray photoelectron spectroscopic measuring instrument manufactured by VG Scientific, UK. (Model name, XPS), the area of the peak representing the metal element derived from the alkoxide when the gas barrier coating film surface after ion sputter etching is measured under the following conditions (for example, when the metal element is Si, 96-104 eV) is a value obtained by dividing the peak area representing the carbon atom derived from the water-soluble polymer (for example, 278-288 eV when the water-soluble polymer is polyvinyl alcohol).
(Measurement condition)
X-ray source: Monochromated Al Kα
X-ray output: 10 kV, 18 mA
Lens: Small Area XL 150
Aperture opening: F.O.V = 3.25, A.A = 4.25
Measurement area: 150μmΦ
Charge neutralization: Electron neutralization gun +4 (V), 0.05 (mA), neutralization assist mask used Photoemission angle: 90 degrees

  Moreover, the surface roughness (Ra) as used in the field of this invention means what was measured according to JIS standard B0601. Such surface roughness (Ra) is measured, for example, by using a scanning probe microscope (SPM) “SPM-9500J3” manufactured by Shimadzu Corporation and measuring the surface of the barrier film at a scanning area of 500 nm × 500 nm at room temperature. Obtainable.

  Next, the material which comprises the gas barrier laminated film of this invention, its manufacturing method, etc. are demonstrated.

Substrate As the substrate constituting the gas barrier laminate film of the present invention, it has excellent chemical or physical strength, withstands the conditions for forming an inorganic oxide vapor deposition film, etc., and the properties of the inorganic oxide vapor deposition 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 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.

Next, the vapor deposition film which comprises the gas barrier laminated film of this invention is demonstrated. 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, 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 by 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, a vapor deposition monomer gas such as oxygen gas, inert gas, or organosilicon compound 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 to} 1.33 × 10 ⁻⁸ mbar, preferably the degree of vacuum is 1.33 × 10 ^{−3 to} 1.33 × 10 ^−. It is preferable to adjust to ⁷ mbar.

  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 conveyed at a constant speed, and glow discharge plasma causes the cooling / electrode drum surface to be conveyed. 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 it is preferable to adjust the conveyance speed of the resin film to 10 to 300 m / min, 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, the vacuum degree during formation of a continuous film of an inorganic oxide such as silicon oxide as described ^{above, 1.33 × 10 -1 ~1.33 × 10} -4 mbar, preferably 1.33 × 10 ^-1 Since it is adjusted to ˜1.33 × 10 ⁻² mbar, the vacuum is lower than the degree of vacuum (1.33 × 10 ^{−4 to} 1.33 × 10 ⁻⁵ mbar) when forming a deposited film by conventional vacuum deposition. Therefore, it is possible to shorten the vacuum state setting time at the time of exchanging the original film or sheet of the resin, the degree of vacuum is stabilized, and the film forming process is stabilized.

  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.

  As the above-described silicon oxide vapor deposition film, silicon oxide vapor deposition represented by the general formula: SiOx (wherein x represents the number of 1.3 to 1.9) is required from the viewpoint of transparency and barrier properties. A thin film mainly composed of a 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, etc. It becomes difficult to stably maintain the 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 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, a base film obtained by forming the first layer and the second silicon oxide layer in the second film forming chamber is formed into a 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 arranged 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} 1.33. It is preferable to adjust to × 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 for cooling and 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 adjusted to 10-300 m / min, Preferably it is 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-forming consisting of one kind of organosilicon compound is 1 to 40%, and the content of oxygen gas is 0. It is preferable to adjust the content of ˜70% and inert gas 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 film-forming mixed gas composition having a gas composition ratio of 0 to 5: 1 (unit: Slm, an abbreviation for standard liter minute), and another second film-forming mixed gas composition include: Film-forming monomer gas: oxygen gas: inert gas = 1: 6 to 15: 1 (unit: Slm) 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. (Physical Vapor Deposition method, PVD method) can be used.

  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 about 100 to 1000 mm. It is desirable to select and form arbitrarily within the surroundings.

  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 take-up chamber 81 of the take-up vacuum deposition apparatus 80, the resin film or sheet (base film) 1 fed out from the take-out roll 82 is passed through the guide rolls 83 and 84. To the cooled coating drum 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 deposition 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 deposition film is obtained. 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 the introduction of oxygen gas, and 10 ⁻ after the introduction of oxygen gas. ¹ to 10 ⁻⁶ mbar, preferably 10 ⁻² to 10 ⁻⁵ mbar is desirable. 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.

Next, the gas barrier coating film constituting the gas barrier laminated film of the present invention will be described.
The gas barrier coating film of the present invention contains an alkoxide and a water-soluble polymer. Specifically, as the gas barrier coating film, at least represented by the general formula: R ¹ _n M (OR ² ) _m A gas barrier coating film using a gas barrier composition obtained by polycondensation of a composition containing one or more alkoxides, polyvinyl alcohol and / or ethylene / vinyl alcohol by a sol-gel method is 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 element, 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 element 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 alone or in combination of two or more different metal element 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 thereof 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,} 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 preferably 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 preferably 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 preferably 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, heat resistance and the like of the resulting laminated film are 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 film is lowered, and the heat resistance of the substrate is remarkably 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 as a water-soluble polymer. By combining polyvinyl alcohol and ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance, and the like of the obtained 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 content of the water-soluble polymer is such that the element ratio (M / C) of the metal element (M) derived from the alkoxide and the carbon element (C) derived from the water-soluble polymer in the gas barrier coating film is 2. The amount should be such that 8 <M / C <4.12, preferably 2.8 <M / C <3.4. The content of the water-soluble polymer varies depending on R ¹ , R ² , the type of metal element contained in the alkoxide used, and the type of the water-soluble polymer. For example, normal ethyl silicate is used as the alkoxide. When polyvinyl alcohol is used as the water-soluble polymer, the content of polyvinyl alcohol is in the range of about 45 to 57 parts by weight with respect to 100 parts by weight of the solid content of normal ethyl silicate (SiO ₂ part). Yes, preferably about 47-57 parts by weight.

  The amount of the alkoxide with respect to the water-soluble polymer is excessive, that is, the element ratio (M / C) of the metal element (M) derived from the alkoxide and the carbon element (C) derived from the water-soluble polymer is 4.12. Preferably, when it exceeds 3.4, the crosslinking reaction of alkoxide proceeds excessively and a dense film cannot be formed. As a result, the surface roughness (Ra) of the gas barrier coating film is excessively increased, and the gas barrier property is decreased.

  The amount of alkoxide with respect to the water-soluble polymer is too small, that is, the element ratio (M / C) of the metal element (M) derived from the alkoxide and the carbon element (C) derived from the water-soluble polymer is 2.8. If it is less than 1, the swelling of the water-soluble polymer cannot be suppressed, the surface roughness (Ra) of the gas barrier coating film is excessively increased, and as a result, the gas barrier property is decreased.

  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 the like, 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 catalyst for a sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent or 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 water in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of alkoxide. It is preferable. 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, silane coupling agent, or the like. 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 base film coated with the above coating solution is at a temperature of 20 ° C. to 250 ° C. and below the melting point of the base film, preferably 50 ° C. to 200 ° C., particularly 150 ° C. to 250 ° C. Specifically, inorganic oxidation formed on one side of the base film by heat treatment at a temperature in the range of 180 ° C. to 200 ° C. for 1 second to 10 minutes, preferably 1 second to 2 minutes, particularly 30 seconds to 90 seconds. A gas barrier coating film is formed by forming one or two or more gas barrier coating films of the gas barrier composition (coating liquid) on the vapor deposition film.

  In particular, in the present invention, by performing the above heat treatment at a temperature in the range of 150 ° C. to 250 ° C., preferably 180 ° C. to 200 ° C., the alkoxide hydrolyzate and the water-soluble polymer are formed inside the gas barrier coating film. Gas barrier properties due to the occurrence of cross-linking reactions that occur due to hydrogen bonds or chemical bonds, the crystallization of water-soluble polymers, and the adhesion between the deposited film and the gas barrier coating film due to hydrogen bonds or chemical bonds. In addition, the gas barrier laminate film can be obtained in which the flexibility is improved and damage such as cracks does not occur in the molding process and the like and the high gas barrier property is maintained after the process.

  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.

  Examples of the method for applying the gas barrier coating film forming composition include one or more times by a coating means such as a roll coat such as a gravure coater, a spray coat, a spin coat, a dipping, a brush, a barcode, and an applicator. With this coating, the gas barrier coating film of the present invention having a dry-fired film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm, can be formed.

  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).

Next, as a packaging bag using the present gas barrier laminate film, as an example, a printing layer, an adhesive layer for laminating, and a heat sealable resin layer are sequentially provided on the gas barrier coating film of the gas barrier laminate film. 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.

Next, the laminating adhesive layer constituting the laminated material 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, rubber-based adhesives consisting of styrene-butadiene rubber, a silicone-based 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).

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 a kind of resins such as acid-modified polyolefin resins obtained by modifying these resins with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, and fumaric acid Or a resin film or paper made of more than that It is possible to use the door.

  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, and 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 ”, a trade name“ engage ”, etc., 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 a multilayer, 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, for the reason described above, about 10 to 100 μm, preferably 12 to 50 μm is preferable.

  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. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.

  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) Formation of Vapor Deposition Film by Physical Vapor Deposition Method A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as a base film, and first, the above-mentioned biaxially stretched polyethylene terephthalate film is wound up and vacuum-deposited Attached to the feeding roll. Next, this was fed out, and the following vapor deposition conditions were applied by a vacuum vapor deposition method using an electron beam heating method (EB) while supplying oxygen gas to the corona-treated surface of the biaxially stretched polyethylene terephthalate film using aluminum as a vapor deposition source. Thus, a vapor deposition film of aluminum oxide having a thickness of about 200 mm was formed.
(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-treated surface

After that, a glow discharge plasma generator was used on the vapor deposition film surface of aluminum oxide, a mixed gas consisting of power 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: Slm), and 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 aluminum oxide deposition film surface was improved by 54 dyne / cm or more.

(2) Formation of gas barrier coating film On the other hand, according to the composition shown in Table 1, composition a. Composition b prepared in advance in a hydrolyzed solution consisting of orthoethyl silicate (manufactured by Tama Kagaku Co., solid content (SiO ₂ min 28%), isopropyl alcohol, 0.5 N hydrochloric acid aqueous solution, ion-exchanged water and silane coupling agent) . A polyvinyl alcohol aqueous solution composed of polyvinyl alcohol, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier coating solution.
In the table, the concentration of each sample is expressed in weight%.

  Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by a gravure roll coating method, and then heat-treated at 200 ° C. for 60 seconds to obtain a thickness of 0 A gas barrier coating film of .2 μm (in the dry operation state) was formed to produce a gas barrier laminated film of the present invention.

[Comparative Examples 1 to 7]
The gas barrier laminated films of Comparative Examples 1 to 7 were produced in the same manner as in Example 1 except that the composition of the gas barrier composition was as shown in the following table. In the table, the concentration of each sample is expressed in weight%.

[Example 2]
(1) Formation of vapor-deposited film by chemical vapor deposition method A biaxially stretched polyester film having a thickness of 12 μm is used as a base film, and this is mounted on a delivery roll of a plasma chemical vapor deposition apparatus, and the conditions shown below Then, a vapor-deposited film of silicon oxide having a thickness of about 100 mm was formed on the corona-treated surface of the above biaxially stretched polyester film.
(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

Then, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and a mixed gas consisting of power 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm). Plasma treatment with oxygen / argon mixed gas plasma treatment at a mixed gas pressure of 6 × 10 ⁻² mbar and a treatment speed of 420 m / min to improve the surface tension of the deposited film surface of silicon oxide by 54 dyne / cm or more. A surface was formed.

(2) Formation of gas barrier coating film On the other hand, according to the composition shown in Table 3, the composition a. Composition b prepared in advance in a hydrolyzed solution consisting of orthoethyl silicate (manufactured by Tama Kagaku Co., solid content (SiO ₂ min 28%), isopropyl alcohol, 0.5 N hydrochloric acid aqueous solution, ion-exchanged water and silane coupling agent) . A polyvinyl alcohol aqueous solution composed of polyvinyl alcohol, isopropyl alcohol and ion-exchanged water was added and stirred to obtain a colorless and transparent gas barrier coating solution.
In the table, the concentration of each sample is expressed in weight%.

  Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by a gravure roll coating method, and then heat-treated at 200 ° C. for 60 seconds to obtain a thickness of 0 A gas barrier coating film of .2 μm (in the dry operation state) was formed to produce a gas barrier laminated film of the present invention.

[Comparative Examples 8-14]
The gas barrier laminated films of Comparative Examples 8 to 14 were produced in the same manner as in Example 2 except that the composition of the gas barrier composition was as shown in the following table. In the table, the concentration of each sample is expressed in weight%.

[Experimental example]
1. Measurement of element ratio of silicon element in normal ethyl silicate and carbon element in polyvinyl alcohol contained in gas barrier coating film Gas barrier coating of gas barrier laminated films of Examples 1 and 2 and Comparative Examples 1-14 The film surface was subjected to ion sputtering etching. Next, the surface of the gas barrier coating film of each of the above Examples and Comparative Examples was measured under the following conditions using an X-ray photoelectron spectroscopic analyzer (model name, XPS) manufactured by VG Scientific, UK. . Thereafter, the peak area of 96 to 104 eV representing silicon element in normal ethyl silicate is divided by the peak area of 278 to 288 eV representing carbon element in polyvinyl alcohol, and each of the gas barrier coating films of Examples and Comparative Examples is used. The element ratio (Si / C ratio) of the silicon element in the contained normal ethyl silicate and the carbon element in the polyvinyl alcohol was calculated.
(Measurement condition)
X-ray source: Monochromated Al Kα
X-ray output: 10 kV, 18 mA
Lens: Small Area XL 150
Aperture opening: F.O.V = 3.25, A.A = 4.25
Measurement area: 150μmΦ
Charge neutralization: Electron neutralization gun +4 (V), 0.05 (mA), neutralization assist mask used Photoemission angle: 90 degrees

2. Measurement of Surface Roughness (Ra) Using a scanning probe microscope (SPM) “SPM-9500J3” manufactured by Shimadzu Corporation, according to JIS standard B0601, the gas barrier coating film surfaces of Examples 1 and 2 and Comparative Examples 1 to 14 were measured. Surface shape observation was performed at a scanning area of 500 nm × 500 nm at room temperature. Next, the average surface roughness (Ra) of the observed surface shape was determined by surface roughness analysis software in the apparatus.

3. Measurement of Oxygen Permeability The gas barrier laminate films produced in Examples 1 and 2 and Comparative Examples 1 to 14 were measured under the conditions of a temperature of 23 ° C. and a humidity of 90% RH. The oxygen permeability was measured according to JIS standard K7126 using a model name “OXTRAN”.

4). Measurement of water vapor transmission rate The gas barrier laminate films produced in Examples 1 and 2 and Comparative Examples 1 to 14 were measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. Water vapor permeability was measured according to JIS standard K7129 using a model name “PERMATRAN”.

  The results of the above experimental examples 1 to 4 are shown in the following (Table 5), and the relationship between the Si / C ratio and the surface roughness (Ra) or water vapor permeability is shown in FIG.

"Measurement result"
As shown in the above (Table 5), the gas barrier laminated films of Examples 1 and 2 had excellent gas barrier properties as compared with Comparative Examples 1-14.

For example, in the gas barrier laminate film of Example 1, the ratio (Si / C value) of the silicon element derived from the alkoxide and the carbon element derived from the polymer contained in the gas barrier coating film is 3.12. Although the surface roughness (Ra) of the gas barrier coating film surface is as low as 0.195 (nm), its water vapor permeability is as low as 0.58 (g / m ² · day), and an excellent water vapor barrier. It was confirmed to have sex.

On the other hand, the gas barrier laminate film of Comparative Example 1 has a low Si / C value of 1.29 and a high surface roughness (Ra) of 0.365 (nm). The degree was as high as 1.19 (g / m ² · day), and it was confirmed that the water vapor barrier property was inferior to that of the example.

Furthermore, the gas barrier laminate film of Comparative Example 7 has a high Si / C value of 6.04 and a surface roughness (Ra) as high as 0.582 (nm). It was as high as 0.64 (g / m ² · day), and it was confirmed that the water vapor barrier property was inferior to that of the example.

On the other hand, the gas barrier laminate film of Example 2 is a film formed by chemical vapor deposition and has a Si / C value of 3.12. The oxygen permeability and water vapor permeability are as follows. It was confirmed to have an excellent gas barrier property with low values of 0.06 (cc / m ² · day) and 0.53 (g / m ² · day), respectively.

On the other hand, the gas barrier laminate film of Comparative Example 8 has a low Si / C value of 1.29, and its oxygen permeability and water vapor permeability are each 0.30 (cc / m ² · (day) and 1.18 (g / m ² · day), which were high, and it was confirmed that the gas barrier properties were inferior to those of Examples.

Furthermore, the gas barrier laminate film of Comparative Example 14 has a high Si / C value of 6.04, but its oxygen permeability and water vapor permeability are 0.24 (cc / m ² · day), 0 It was as high as .76 (g / m ² · day), and it was confirmed that the gas barrier properties were inferior to those of Examples.

  Further, as is clear from FIG. 6, as the Si / C value approaches 3, the surface roughness (Ra) of the gas barrier coating film surface is reduced, and at the same time, the water vapor barrier property is improved.

  That is, by making the element ratio (M / C) of the metal element (M) derived from the alkoxide in the gas barrier coating film and the carbon element (C) derived from the water-soluble polymer constant, it becomes denser, In addition, as a result of forming a strong three-dimensional network composite polymer layer, it was confirmed that a gas barrier laminate film having a significantly higher gas barrier property than that of the conventional one can be obtained.

  Moreover, it was confirmed that a gas barrier laminate film having a higher gas barrier property can be obtained by forming a deposited film by chemical vapor deposition.

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 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 apparatus 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 3 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 Volatile supply device 57 Supply device 58 Raw material supply nozzle 59 Glow discharge plasma 60, 61 Auxiliary roll 62 Cooling / electrode drum 63 Raw material volatilization supply device 64 Gas supply device 65 Raw 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 Winding 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 (11)

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,
The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal element, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and n is 0 or more) A composition comprising at least one alkoxide, polyvinyl alcohol and / or ethylene / vinyl alcohol represented by: m is an integer of 1 or more, and n + m represents a valence of M). , An alkoxide hydrolyzate obtained by polycondensation by a sol-gel method, or a gas barrier coating film by an alkoxide hydrolysis condensate,
Here, the element ratio (Atomic%) of the metal element (M) derived from the alkoxide in the gas barrier coating film and the carbon element (C) derived from polyvinyl alcohol and / or ethylene / vinyl alcohol,
2.8 <M / C <4.12
The gas barrier laminate film as described above. The element ratio (Atomic%) of the metal element (M) derived from the alkoxide in the gas barrier coating film and the carbon element (C) derived from polyvinyl alcohol and / or ethylene / vinyl alcohol,
2.8 <M / C <3.4
The gas barrier laminate film according to claim 1, wherein: The gas barrier coating film has a surface roughness (Ra) of
0.15 (nm) <Ra <0.275 (nm)
The gas barrier laminate film according to claim 1, wherein:   The gas barrier laminate film according to any one of claims 1 to 3, wherein the vapor-deposited film of the inorganic oxide is formed by a chemical vapor deposition method or a physical vapor deposition method.   The gas barrier according to any one of claims 1 to 4, wherein the metal element (M) contained in the alkoxide in the gas barrier property is selected from the group consisting of silicon, zirconium, titanium, and aluminum. Laminated film.   The gas barrier coating film according to claim 1, wherein the gas barrier coating film further contains a silane coupling agent. It is a manufacturing method of the gas barrier lamination film according to any one of claims 1 to 6,
An inorganic oxide vapor-deposited film is formed on the substrate, and a gas barrier coating film [wherein the gas barrier coating film is represented by the general formula R ¹ _n M (OR ² ) _m (wherein , M represents a metal element, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, n is an integer of 0 or more, m is an integer of 1 or more, and n + m represents the valence of M. A hydrolyzate of alkoxide or hydrolytic condensation of alkoxide obtained by polycondensation of a composition comprising at least one alkoxide, polyvinyl alcohol, and / or ethylene vinyl alcohol represented by sol-gel method A gas barrier coating film made of a material, and a metal element (M) derived from an alkoxide in the gas barrier coating film and a charcoal derived from polyvinyl alcohol and / or ethylene / vinyl alcohol. Element ratio of the element (C) (Atomic%) is,
2.8 <M / C <4.12
It shall be]
A method for producing the gas barrier laminate film, comprising forming a film. The element ratio (Atomic%) of the metal element (M) derived from the alkoxide in the gas barrier coating film and the carbon element (C) derived from polyvinyl alcohol and / or ethylene / vinyl alcohol,
2.8 <M / C <3.4
The method for producing a gas barrier laminate film according to claim 7.   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.   A packaging laminate using the gas barrier laminate film according to claim 1, wherein a printing layer, a laminate adhesive layer, and a heat sealable resin layer are provided on the gas barrier coating film of the laminate film. A laminated material for packaging characterized in that.   A packaging bag using the packaging laminate according to claim 9 or 10, wherein one side of the packaging laminate is a heat-sealable resin layer side, and the other side of the packaging laminate is a heat-sealable resin layer side. The packaging bag is characterized in that it is overlapped so as to face each other and its end is heat sealed.

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