JP2005119155A - Gas barrier film and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film having high barrier properties in spite of reduced film thickness and not lowering gas barrier properties with respect to gas such as oxygen, steam or the like even under a much moisture condition, and its manufacturing method. <P>SOLUTION: This gas barrier film has a base material film and a silicon oxide film formed on one side or both sides of the base material film by a plasma CVD method. The silicon oxide film has a component ratio wherein the number of oxygen atoms is 170-200 and the number of carbon atoms is 30 or below with respect to the number of silicon atoms of 100 and has an IR absorption based on Si-O-Si expansion and contraction vibration between wavelengths of 1055-1065 cm<SP>-1</SP>. At least one composite polymer layer wherein a main component comprises a straight chain polymer obtained by the polycondensation of a composition containing an alkoxysilane, a silane coupling agent and a polyvinyl alcohol by a sol-gel method is laminated on the silicon oxide film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a high barrier film and a method for producing the same, and more specifically, a gas barrier film having a high barrier property that prevents permeation of oxygen, water vapor, and the like, and further prevents cracking due to bending, stretching, and the like, and It relates to the manufacturing method.

  The gas barrier film is mainly used as a packaging material for food and pharmaceuticals to prevent the influence of oxygen and water vapor, which cause the quality of the contents to change, and is formed on liquid crystal display panels and EL display panels. In order to avoid degradation of the performance of the element being exposed to oxygen or water vapor, it is used as a packaging material for electronic devices and the like. In recent years, gas barrier films are sometimes used for the purpose of imparting flexibility and impact resistance to portions that have been conventionally used as packaging materials for devices such as glass.

  Such a gas barrier film generally has a structure in which a plastic film is used as a base film and a gas barrier layer is formed on one side or both sides thereof. The gas barrier film is formed by various methods such as a CVD method, a PVD method, and a sputtering method. Even if any method is used, the conventional gas barrier film has its oxygen permeability and water vapor. The transmittance was still insufficient when used in applications requiring higher gas barrier properties.

As a method of dry-forming a film having gas barrier properties on a plastic substrate film, a method of forming a silicon oxide film or an aluminum oxide film using a dry film-forming method such as a plasma CVD method is known (for example, a patent) Reference 1, Patent Document 2, and Patent Document 3). In particular, the plasma CVD method has an advantage that a silicon oxide film or an aluminum oxide film having excellent gas barrier properties and flexibility can be formed without causing thermal damage to the plastic substrate film. Furthermore, it has a component ratio of 170 to 200 oxygen atoms and 30 or less carbon atoms with respect to 100 silicon atoms on one or both sides of the base film, and further Si—O—Si between 1055 to 1065 cm ^−1. A gas barrier film provided with a silicon oxide film formed by a plasma CVD method and having IR absorption based on stretching vibration is known (see Patent Document 4).
JP-A-8-176326 Japanese Patent Laid-Open No. 11-309815 JP 2000-6301 A JP 2002-192646 A

  However, although the thing of this patent document 4 is excellent in gas barrier property, it is inadequate for the use for which a thinner film thickness is requested | required.

  An object of the present invention is to provide a gas barrier film having a high barrier property and a barrier property against a gas such as oxygen and water vapor, and a method for producing the same, even though the gas barrier film has a thin film thickness. Is to provide.

The invention according to claim 1 solves the above-described problems of the invention relating to the gas barrier film, and includes a base film and a silicon oxide film formed on one side or both sides of the base film by a plasma CVD method. The silicon oxide film has a component ratio of 170 to 200 oxygen atoms and 30 or less carbon atoms to 100 silicon atoms, and further exhibits Si—O—Si stretching vibration between 1055 to 1065 cm ^−1. The main component is linear, obtained by polycondensation of a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol on the silicon oxide film by a sol-gel method. The gist of the present invention is a gas barrier film in which at least one composite polymer layer made of a polymer is laminated.

  In the first aspect of the present invention, a silicon oxide film having extremely excellent gas barrier properties is formed by controlling the component ratio and IR absorption characteristics of the silicon oxide film within the above ranges.

  In the first aspect of the present invention, the silicon oxide film desirably has a refractive index of 1.45 to 1.48. By controlling the refractive index of the silicon oxide film within the above range, the gas barrier property is further improved, and a silicon oxide film exhibiting excellent gas barrier property is formed. The gas barrier film according to the first aspect of the present invention is provided with a silicon oxide film exhibiting excellent gas barrier properties, and the gas barrier properties are further enhanced by the composite polymer layer.

  According to the invention described in claim 1, the film thickness of the silicon oxide film is set to, for example, 50 nm, and the film thickness of the composite polymer layer is set to 2 μm. In addition, it is possible to provide a gas barrier film that has a high barrier property and that does not deteriorate a barrier property against a gas such as oxygen or water vapor even in a humid environment of 90% RH.

  Invention of Claim 3 solves the subject regarding the said gas barrier film, and is formed by the plasma CVD method on one side or both sides of the base film and the base film, and has an interval of 5 to 40 nm on the surface. The main component is obtained by polycondensation of a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol on the vapor deposition film by a sol-gel method. The gist of the present invention is a gas barrier film in which at least one composite polymer layer made of a chain polymer is laminated.

  In the invention according to claim 3, a silicon oxide film can be preferably used as the vapor deposition film.

  In the invention according to claim 3, by controlling the distance between the grains of the vapor deposition film within the above range, the region through which the gas can permeate can be reduced, and a vapor deposition film having an extremely excellent gas barrier property is formed. The The gas barrier film according to the invention described in claim 3 is provided with a vapor-deposited film exhibiting excellent gas barrier properties, and the gas barrier properties are further enhanced by the composite polymer layer.

  According to the invention described in claim 3, the film thickness of the silicon oxide film is set to, for example, 50 nm, and the film thickness of the composite polymer layer is set to 2 μm. In addition, it is possible to provide a gas barrier film that has a high barrier property and that does not deteriorate a barrier property against a gas such as oxygen or water vapor even in a humid environment of 90% RH.

Invention of Claim 5 solves the subject regarding said gas barrier property, and is formed by the plasma CVD method on one side or both sides of this base film and this base film, and is observed by the electron spin resonance method A silicon oxide film having an E ′ center and a density of the E ′ center of 5 × 10 ¹⁵ spins / cm ³ or more. On the silicon oxide film, an alkoxysilane, a silane coupling agent and polyvinyl The gist of the present invention is a gas barrier film obtained by laminating at least one composite polymer layer, the main component of which is a linear polymer, obtained by polycondensation of a composition containing alcohol by a sol-gel method.

In the invention according to claim 5, since the silicon oxide film has an E ′ center, that is, an unpaired electron, and has a structure in which the film is closely dented, it exhibits extremely excellent gas barrier properties. In that case, a silicon oxide film having an E ′ center density of 5 × 10 ¹⁵ spins / cm ³ or more certainly has a structure in which the structure of the film is densely distorted. The performance is very good. The gas barrier film according to the invention of claim 5 includes the silicon oxide film exhibiting excellent gas barrier properties as described above, and further has a gas barrier property enhanced by a composite polymer layer.

  According to the invention described in claim 5, the film thickness of the silicon oxide film is set to, for example, 50 nm, and the composite polymer layer is set to 2 μm, so that the barrier is higher than the gas barrier film described in Patent Document 4 while being a thin film. In addition, it is possible to provide a gas barrier film that has a property and does not deteriorate a barrier property against a gas such as oxygen or water vapor even in a humid environment of 90% RH.

Invention of Claim 6 solves the subject regarding said gas barrier film, has a base film, and a silicon oxide film formed by plasma CVD method on one side or both sides of the base film, The silicon oxide film has an IR absorption peak based on the stretching vibration of CO molecules at 2341 ± 4 cm ⁻¹ , and a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol is formed on the silicon oxide film. The gist of the present invention is a gas barrier film obtained by laminating at least one composite polymer layer comprising a linear polymer as a main component, obtained by polycondensation by a sol-gel method.

In the gas barrier film of the invention described in claim 6, since the silicon oxide film has an IR absorption peak based on the stretching vibration of CO molecules at 2341 ± 4 cm ⁻¹ , it exhibits extremely excellent gas barrier properties. The gas barrier film according to the invention of claim 6 includes a silicon oxide film that exhibits excellent gas barrier properties, and further has a gas barrier property enhanced by a composite polymer layer.

  According to the invention described in claim 6, the film thickness of the silicon oxide film is set to, for example, 50 nm, and the film thickness of the composite polymer layer is set to 2 μm. In addition, it is possible to provide a gas barrier film that has a high barrier property and that does not deteriorate a barrier property against a gas such as oxygen or water vapor even in a humid environment of 90% RH.

  In the gas barrier film according to any one of claims 1 to 6, the thickness of the silicon oxide film is 5 to 300 nm, preferably 5 to 50 nm. The silicon oxide film exhibits not only excellent gas barrier properties even when the film thickness is 5 to 50 nm, but also exhibits extremely high gas barrier properties by laminating a composite polymer layer on the thin silicon oxide film. Moreover, cracks can be prevented from entering by making the film thinner. Further, such a thinned silicon oxide film has excellent transparency, appearance, and the like, and can suppress an increase in curling of the film, which is preferable in terms of productivity.

  In the present invention, the composition containing an alkoxysilane, a silane coupling agent, and polyvinyl alcohol forming a composite polymer may further contain one or more metal alkoxides.

  Invention of Claim 9 solves the subject regarding the manufacturing method of said gas barrier film, The gas containing the organic silicon compound which does not have a carbon-silicon bond in a molecule | numerator, and the gas containing an oxygen atom are source gas The gas flow ratio between the organosilicon compound gas and the oxygen atom-containing gas is introduced into the reaction chamber in the range of 1: 3 to 1:50, and oxidized by plasma CVD on the substrate film placed in the reaction chamber. The process of forming a silicon film, and after the film formation, a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol on the silicon oxide film is present in the presence of a sol-gel catalyst, mineral acid, water, and an organic solvent. A process of applying a coating liquid containing a composite polymer of the composition, the main component of which is a linear polymer, obtained by polycondensation below, and then a coating film of the coating liquid And gist of the method for producing a gas barrier film, which comprises forming a composite polymer layer of the composition on the silicon oxide film and subjected to heat treatment at a temperature below the melting point of the base film at 120 ° C. or higher.

  According to the above manufacturing method, a gas barrier film having a high barrier property and having a low barrier property against a gas such as oxygen or water vapor even under a high humidity condition is manufactured while being a thin gas barrier film. can do.

  In said manufacturing method, you may use the said composition containing 1 or more types of metal alkoxide further as a composition containing an alkoxysilane, a silane coupling agent, and polyvinyl alcohol.

  In the production method described above, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used as a sol-gel method catalyst for polycondensation of the composition.

  Furthermore, in the above production method, water used when the composition is combined with the composition is used in a ratio of 0.8 mol to 2 mol with respect to 1 mol of alkoxysilane. Moreover, when the said composition contains a metal alkoxide, it is used in the ratio of 0.8 mol or more and 2 mol or less with respect to 1 mol of total moles of an alkoxide and a metal alkoxide. When the amount of water exceeds 2 mol, the polymer obtained from the alkoxysilane or 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. It becomes. The gas barrier property cannot be enhanced by this porous polymer. When the amount of water is less than 0.8 mol, the hydrolysis reaction hardly proceeds.

  Furthermore, in the above production method, the composite polymer layer is subjected to an acetal treatment (treatment of immersing the gas barrier film on which the composite polymer layer is formed in an aldehyde solution) as necessary. By this acetal treatment, an unreacted hydroxyl group caused by PVA present in a minute amount in the composite polymer reacts with the aldehyde to be acetalized, and the water resistance (moisture resistance) of the composite polymer is further improved.

According to the invention of claim 1, claim 3, claim 5 and claim 6, the number of oxygen atoms is 170-200 and the number of carbon atoms is 30 or less with respect to the number of silicon atoms of 100 formed by the plasma CVD method. A silicon oxide film having a component ratio and having IR absorption based on Si—O—Si stretching vibration between 1055 and 1065 cm ⁻¹ , a grain formed by a plasma CVD method and having a surface with a spacing of 5 to 40 nm A silicon oxide film having an E ′ center observed by an electron spin resonance method and having a density of 5 × 10 ¹⁵ spins / cm ³ or more, formed by a plasma CVD method, or was formed by a plasma CVD method, a silicon oxide film and the alkoxysilane having an IR absorption peak based on the stretching vibration of CO molecules in 2341 ± 4 cm ^-1, A thin gas barrier film obtained by laminating at least one composite polymer layer comprising a linear polymer as a main component, obtained by polycondensing a composition containing a run coupling agent and polyvinyl alcohol by a sol-gel method. However, it has a high barrier property, does not deteriorate the barrier property against gases such as oxygen and water vapor even under high humidity conditions, and is excellent in water resistance, flexibility, solvent resistance and resistance. A gas barrier film excellent in chemical properties can be provided.

  Further, the production method of the present invention uses a gas containing an organic silicon compound having no carbon-silicon bond in the molecule and a gas containing oxygen atoms as a raw material gas, and a gas containing an organic silicon compound and a gas containing oxygen atoms. A process of forming a silicon oxide film by a plasma CVD method on a base film introduced into the reaction chamber with a flow rate ratio of 1: 3 to 1:50 and disposed in the reaction chamber, and a post-deposition silicon oxide film The main component is a linear polymer obtained by polycondensation of a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol in the presence of a sol-gel method catalyst, mineral acid, water, and an organic solvent. And a step of applying a coating solution containing the composite polymer of the composition, and then subjecting the coating film of the coating solution to heat treatment at a temperature of 120 ° C. or higher and lower than the melting point of the base film. The process comprises the step of forming a composite polymer layer of the composition on a silicon film. According to this production method, although it is a thin film barrier film, it has a high barrier property and oxygen or water vapor even under humid conditions. It is possible to produce a gas barrier film that does not deteriorate the barrier properties against gases such as, has excellent water resistance, is flexible, and has excellent solvent resistance and chemical resistance.

  Next, the gas barrier film of the present invention will be described with reference to the drawings.

(First embodiment: Embodiment of the invention described in claim 1)
FIG. 1 shows a gas barrier film according to the first aspect of the present invention. This gas barrier film has a base film 1 and a silicon oxide film 2 formed on one surface of the base film 1 by a plasma CVD method. In the embodiment shown in FIG. 1, the silicon oxide film 2 is provided only on one side of the base film 1, but the silicon oxide film 2 may be provided on both sides of the base film 1. The silicon oxide film 2 has a component ratio of 170 to 200 oxygen atoms and 30 or less carbon atoms to 100 silicon atoms, and is further based on Si—O—Si stretching vibration between 1055 and 1065 cm ^−1. It has IR absorption. Furthermore, a composite polymer layer whose main component is a linear polymer obtained by polycondensation of a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol on the silicon oxide film 2 by a sol-gel method. 3 (hereinafter referred to as composite polymer layers) are laminated. In the gas barrier film according to the first aspect of the present invention, a gas barrier layer comprising two layers of a silicon oxide film and a composite polymer layer is formed. Therefore, the silicon oxide film not only exhibits excellent gas barrier properties even when the film thickness is 5 to 50 nm, but also exhibits extremely high gas barrier properties by laminating a composite polymer layer on the thin silicon oxide film. It is done. Moreover, cracks can be prevented from entering by making the film thinner. Further, such a thinned silicon oxide film has excellent transparency, appearance, and the like, and can suppress an increase in curling of the film, which is preferable in terms of productivity. Hereinafter, the base film 1, the silicon oxide film 2, and the composite polymer layer 3 will be described.

(A) Base film The base film 1 is not particularly limited as long as it can hold the silicon oxide film 2, and any film can be applied.

In particular,
-Polyolefin resins (PO) such as homopolymers or copolymers such as ethylene, polypropylene, butene,
-Amorphous polyolefin resin (APO) such as cyclic polyolefin,
Polyester resins such as polyethylene terephthalate (PET) and polyethylene 2,6-naphthalate (PEN)
-Polyamide alcohol resins such as nylon 6, nylon 12, copolymer nylon (PA), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), etc.,
・ Polyimide (PI),
-Polyetherimide (PEI),
・ Polysulfone (PS),
・ Polyethersulfone (PES),
・ Polyetheretherketone (PEEK),
・ Polycarbonate (PC),
-Polyvinyl butyrate (PVB),
・ Polyarylate (PAR),
・ Ethylene-tetrafluoroethylene copolymer (ETFE), trifluorochloroethylene resin (PFA), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride resin (PVDF), fluoride Fluorine resins such as vinyl resin (PVF) and perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA) can be used.

  In addition to the above-described resins, a resin compound comprising an acrylate compound having a radical reactive unsaturated compound, a resin composition comprising the acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, poly It is also possible to use a photocurable resin such as a resin composition obtained by dissolving an oligomer such as ether acrylate in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 type, or 2 or more types of these resin by means, such as a lamination and a coating, as a base film.

  The base film described above may be either an unstretched film or a stretched film.

  The base film 1 can be manufactured by a conventionally known general method using the above materials. For example, an unstretched base film 1 that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. In addition, the unstretched base film is uniaxially stretched, tenter-type sequential biaxial stretch, tenter-type simultaneous biaxial stretch, tubular-type simultaneous biaxial stretch, and the like in a flow direction (vertical axis Direction), or a film stretched by stretching in a direction perpendicular to the flow direction of the base film 1 (horizontal axis direction) can be used as the base film. Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the base film 1, it is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.

  The base film 1 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc. before forming the silicon oxide film.

Further, an anchor coat layer may be formed on the surface of the base film 1. As an anchor coating agent, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, alkyl titanate, etc. Can be used together. Conventionally known additives can be added to these anchor coating agents. The anchor coating agent can be applied to the base film 1 by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating or the like. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

(B) Silicon oxide film The silicon oxide film 2 is formed on the base film 1 by a plasma CVD method, and has a component ratio of 170 to 200 oxygen atoms and 30 or less carbon atoms to 100 silicon atoms. Further, the silicon oxide film has IR absorption based on Si—O—Si stretching vibration between 1055 and 1065 cm ⁻¹ . That is, the silicon oxide film 2 exhibits extremely excellent gas barrier properties by controlling the component ratio of the silicon oxide film and the IR absorption characteristics within the above ranges.

  The silicon oxide film 1 is preferably formed to have a refractive index of 1.45 to 1.48. The silicon oxydeposition film having such characteristics exhibits extremely excellent gas barrier properties.

In order to reduce the component ratio of silicon, oxygen, and carbon to 170 to 200 oxygen atoms and 30 or less carbon atoms with respect to 100 silicon atoms, the ratio of the oxygen gas flow rate to the organosilicon compound gas flow rate or the unit flow rate of the organosilicon compound Adjust the amount of input power per hit. In particular, it is desirable to control this adjustment so as to suppress carbon contamination. For example, by adjusting the ratio of the oxygen gas flow rate to the organosilicon compound gas flow rate to about 1 to 3 to 50, it is possible to suppress the mixing of carbon by forming a SiO ₂ like film or per unit flow rate of the organosilicon compound gas. By increasing the input electric power, it is possible to easily cut the Si—C bond and suppress the carbon from being mixed into the film. Note that the upper limit of the flow rate ratio is defined for convenience, and there is no particular problem if it exceeds the upper limit. A silicon oxide film having a component composition in the range of the above flow rate ratio has few Si—C bonds, and thus becomes a SiO ₂ -like homogeneous film and exhibits extremely excellent gas barrier properties. Such component ratios may be any device that can quantitatively measure each component of Si, O, and C. Typical measurement devices include ESCA (Electron Spectroscopy for Chemical Analysis), RBS (Rutherford Back Scattering), Auger It is evaluated by the results measured by electron spectroscopy.

When the number of oxygen atoms with respect to 100 silicon atoms is less than 170, the oxygen gas flow rate to the organosilicon compound flow rate ratio is small (when the oxygen gas flow rate is relatively small compared to the organosilicon gas compound flow rate) or organic This is often seen when the input power per unit flow rate of the silicon compound gas is small, and as a result, the carbon component ratio increases. As a result, the film has many Si—C bonds and is not a SiO ₂ -like homogeneous film, and oxygen permeability and water vapor permeability are increased, and sufficient gas barrier properties cannot be exhibited. Note that the number of oxygen atoms with respect to 100 silicon atoms is less than 200 stoichiometrically. Further, when the number of carbon atoms with respect to 100 silicon atoms exceeds 30, the same conditions as when the number of oxygen atoms with respect to 100 silicon atoms is less than 170, that is, when the ratio of oxygen gas flow rate to organosilicon compound flow rate is small. It is often seen when the oxygen gas flow rate is relatively small compared to the organosilicon gas compound flow rate, or when the input power per unit flow rate of the organosilicon compound gas is small. Remains as it is. As a result, the film has many Si—C bonds and is not a SiO ₂ -like homogeneous film, and oxygen permeability and water vapor permeability are increased, and sufficient gas barrier properties cannot be exhibited.

By making IR (infrared) absorption based on Si—O—Si stretching vibration between 1055 and 1065 cm ^−1, the ratio of oxygen gas flow rate to organosilicon compound gas flow rate is about 1: 3 to 1:50. To make the silicon oxide film a SiO ₂ -like homogeneous film by increasing the magnitude of the input power per unit flow rate of the organosilicon compound gas to facilitate the cutting of the Si-C bond, Can be achieved. The thus formed silicon oxide film exhibiting IR absorption has a Si—O bond peculiar to a SiO ₂ -like homogeneous film, and exhibits extremely excellent gas barrier properties. In contrast, a silicon oxide film that does not exhibit IR absorption has a large oxygen permeability and water vapor permeability and does not exhibit sufficient gas barrier properties. IR absorption is evaluated by measuring with an infrared spectrophotometer for IR measurement. Preferably, an infrared spectrophotometer is attached to an infrared spectrophotometer to measure an infrared absorption spectrum. At this time, it is preferable to use a germanium crystal for the prism and measure at an incident angle of 45 degrees.

The refractive index of the silicon oxide film is adjusted to 1.45 to 1.48 by adjusting the ratio of the oxygen gas flow rate to the organosilicon compound gas flow rate in the range of about 1 to 3 to 1 to 50, and the unit of the organosilicon compound gas. This can be achieved by increasing the magnitude of the input power per flow rate and making the silicon oxide film a SiO ₂ -like homogeneous film. A silicon oxide film having a refractive index in the above range becomes a dense SiO ₂ -like film with few impurities, and exhibits extremely excellent gas barrier properties. On the other hand, a silicon oxide film having a refractive index of less than 1.45 and a silicon oxide film having a refractive index of more than 1.48 have large oxygen permeability and water vapor permeability and do not exhibit sufficient gas barrier properties. Note that the refractive index is obtained by measuring the transmittance and the reflectance with an optical spectrometer and evaluating the refractive index at 633 nm using an optical interference method.

  A silicon oxide film having a thin thickness of 5 to 300 nm not only exhibits excellent gas barrier properties, but also has an advantage that cracks do not easily occur. When the thickness of the silicon oxide film is less than 5 nm, the silicon oxide film that covers the entire surface of the base film may not be formed, and the gas barrier property cannot be improved. On the other hand, when the thickness of the silicon oxide film exceeds 300 nm, cracks are likely to occur, the transparency is lowered, the appearance is deteriorated, the curl of the film is increased, and the mass production is difficult and the productivity is lowered. Inconveniences such as increased costs are likely to occur.

  In the plasma CVD method for forming a silicon oxide film, a raw material at a constant pressure is discharged into a plasma state, and a chemical reaction on the surface of the base film is promoted by active particles generated in the plasma to form a deposited film. It is a method to do. This plasma CVD method can form a film at a low temperature (a temperature in the range of about −10 to 200 ° C.) that does not cause thermal damage to the polymer resin. There is an advantage that the type and physical properties of the film obtained by electric power or the like can be controlled.

  The silicon oxide film 2 supplies a mixture gas of an organosilicon compound gas and an oxygen gas at a predetermined flow rate into a reaction chamber of a plasma CVD apparatus, and applies a constant frequency within a range from DC power or low frequency to high frequency to an electrode. A plasma is generated by applying an electric power, and an organic silicon compound gas is formed on the base film 1 by reacting with a gas having oxygen atoms, particularly an oxygen gas. The type of the plasma CVD apparatus used is not particularly limited, and various types of plasma CVD apparatuses can be used. Usually, a long polymer resin film is used as the base film. An apparatus capable of continuous film formation that can continuously form a silicon oxide film while transporting it is preferably used.

  In this embodiment, the silicon oxide film is transparent, but it is free to arbitrarily laminate a substrate film or other material with poor transparency as a laminated material in order to be used for various applications. The transparency and transparency of the gas barrier film required as a final product vary depending on various applications. For example, when the gas barrier film of this embodiment is used as a packaging material, in order to protect the contents from light rays, the silicon oxide film may be printed with colored ink to provide light shielding properties. In addition, a layer in which an additive such as an antistatic agent or a filler that deteriorates the transparency of the entire gas barrier film is kneaded or a metal foil having no transparency may be laminated. However, when used in applications such as a gas barrier film for a film liquid crystal display, a gas barrier film for a film organic EL display, or a gas barrier film for a film solar cell, the transparency of the entire gas barrier film is required. The effect of the silicon film is great.

(C) Composite polymer layer The composite polymer layer is obtained by polycondensing a composition containing an alkoxysilane, a silane coupling agent and polyvinyl alcohol by a sol-gel method, and the main component is a linear polymer. is there.

  Preferably, the composition further contains one or more metal alkoxides.

The alkoxysilane used in the present invention is represented by Si (OR ¹ ) ₄ , and R ¹ is a lower alkyl group. Specifically, Si (O—CH ₃ ) ₄ , Si (O—C ₂ H ₅ ) ₄ or the like is used. A mixture of these alkoxysilanes may be used.

Moreover, metal alkoxides, such as a zirconium alkoxide and a titanium alkoxide, can be used as a component of a composition with the said alkoxysilane as needed. The zirconium alkoxide is represented by Zr (OR ² ) ₄ and R ² is a lower alkyl group. Specifically, Zr (O—CH ₃ ) ₄ , Zr (O—C ₂ H ₅ ) ₄ , Zr (O—isoC ₃ H ₇ ) ₄ , Zr (O—C ₄ H ₉ ) ₄ are used as metal alkoxides. Etc. can be used. Here, two or more kinds of these metal alkoxides may be mixed and used as a component of the composition. By using zirconium alkoxide as a component of the composition, the toughness and heat resistance of the obtained gas barrier film are improved. The amount 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 the 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 is easily peeled from the silicon oxide film. Next, the titanium alkoxide is represented by Ti (OR ³ ) ₄ and R ³ is a lower alkyl group. Specifically, Ti (O—CH ₃ ) ₄ , Ti (O—C ₂ H ₅ ) ₄ , Ti (O—C ₃ H ₇ ) ₄ , Ti (O—C ₄ H ₉ ) _{4 and the} like are used as a composition. It can be used as a component. Two or more of these alkoxide silanes may be used as a component of the composition. By using titanium alkoxide, the thermal conductivity of the resulting coating is lowered, and the heat resistance of the base film is significantly improved. The amount 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 the alkoxysilane. When the amount exceeds 5 parts by weight, the brittleness of the composite polymer formed becomes large, and the composite polymer from the silicon oxide film is easily peeled off.

  As a silane coupling agent used as a component of the composition together with the alkoxide, a known organic reactive group-containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is suitable. Examples of the organoalkoxysilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. You may mix and use 2 or more types of such a silane coupling agent. The amount of the silane coupling agent used is in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. If an amount of more than 20 parts by weight is used, the rigidity and brittleness of the composite polymer layer formed will increase, and the insulation and workability of the composite polymer layer will decrease.

  In the present invention, polyvinyl alcohol (PVA) is contained in the composition constituting the composite polymer. By adding PVA, the gas barrier properties of the resulting polymer are significantly improved. The content of PVA is in the range of 50 to 200 parts by weight, preferably about 100 parts by weight, with respect to 100 parts by weight of the total amount of the alkoxysilane and metal alkoxide. When the content of PVA exceeds 200 parts by weight with respect to 100 parts by weight of the total amount of the alkoxysilane and metal alkoxide, the brittleness of the composite polymer increases, and the water resistance of the resulting composite polymer layer decreases, resulting in 50 weights. If it is less than%, the gas barrier property is lowered.

  In the present invention, as the sol-gel catalyst used, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Examples thereof include N, N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine, and N, N-dibutylbenzylamine 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 alkoxylane, metal alkoxide, and silane coupling agent. The mineral acid used in the present invention is used not only as a catalyst for the sol-gel method but also as an acetalization catalyst (mainly a hydrolysis catalyst) described later. As the mineral acid, sulfuric acid, hydrochloric acid, nitric acid and the like are used. The amount of mineral acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of alkoxysilane, metal alkoxide, and alkoxide content of the silane coupling agent (silicate portion). It is.

  In the present invention, 0.8 to 2 mol of water is used with respect to the total molar amount of the alkoxysilane and metal alkoxide. When the amount of water exceeds 2 mol, the composite polymer containing the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles crosslink three-dimensionally to form a porous polymer with low density. The composite polymer layer composed of the porous polymer does not provide a gas barrier film having a high gas barrier property. On the other hand, when the amount of water is less than 0.8 mol, the hydrolysis reaction hardly proceeds.

  As the organic solvent used in the present invention, ethyl alcohol, isopropyl alcohol, butyl alcohol and the like are used. The amount of the solvent used is 30 to 100 parts by weight per 100 parts by weight of the total amount of the usual alkoxysilane, metal alkoxide, silane coupling agent, PVA, mineral acid, and sol-gel method catalyst.

  The gas barrier film of the present invention is formed as follows. First, the said alkoxysilane, a silane coupling agent, PVA, a sol-gel method catalyst, a mineral acid, water, an organic solvent, and a metal alkoxide as needed are mixed and a coating liquid is prepared. In this coating solution, the polycondensation reaction gradually proceeds.

  Next, the coating liquid is applied onto the silicon oxide film formed on the base film and dried. By the drying, the polycondensation of the alkoxysilane, metal alkoxide, silane coupling agent, and PVA further proceeds to form a composite polymer layer. Preferably, the above coating and drying operations are repeated to laminate a plurality of composite polymer layers. Finally, when the film coated with the coating solution is heated at 120 ° C. or higher and below the melting point of the base film, preferably at a temperature in the range of 150 to 200 ° C. for 30 seconds to 10 minutes, the present invention The gas barrier film is obtained. The gas barrier film of the present invention thus obtained is subjected to an acetalization treatment as necessary. Specifically, the film on which the composite polymer layer is laminated is immersed in an aldehyde solution containing an acid. By performing acetalization treatment using formaldehyde, acetaldehyde, butyraldehyde, etc. as the aldehyde, the unreacted hydroxyl group caused by PVA present in a minute amount in the composite polymer reacts with the aldehyde to be acetalized, and the water resistance ( Moisture resistance) is further improved.

  As described above, the gas barrier film of the present invention has a high barrier property against oxygen, water vapor and the like while being a thin gas barrier film, and further, the barrier property against gas such as oxygen and water vapor is lowered even under humid conditions. Since it has the advantage that it does not, it is useful not only for packaging materials such as food, tobacco and toiletries, but also for gas barrier films for film liquid crystal displays, gas barrier films for film organic EL displays, gas barrier films for solar cells, etc. It is used for

(Second Embodiment: Embodiment of Invention of Claim 3)
Next, an embodiment of the invention described in claim 3 will be described with reference to FIGS. This embodiment comprises a base film 1, a vapor deposition film 4 and a composite polymer layer 3 in the same manner as the gas barrier film of the invention described in claim 1, provided that the vapor deposition film 4 is shown in FIGS. As shown, the deposited film is a deposited film formed on one or both sides of the base film by the plasma CVD method, and a grain 4a (grain) is formed on the surface of the deposited film 4 with an interval of 5 to 40 nm. It is characterized by being.

The portion of the grain 4a is a portion having high crystallinity in the deposited film, and has a property that gas and water vapor are hardly transmitted. Therefore, by setting the distance L between the grains within the above range, the area through which the gas or the like can pass through the deposited film 4, that is, the area other than the grains becomes small, so that the barrier property can be improved. When the distance L between grains is 5 to 40 nm, a deposited film having a good barrier property can be formed. The distance L between grains
Is more preferably 10 to 30 nm.

  Here, the grain 4a formed on the surface of the vapor deposition film 4 will be described. Grain is an island-shaped projection when a cross section of an AMF image obtained by observing the surface of a silicon oxide film with an atomic force microscope (AFM) is cut at a predetermined height and binarized. The part that appears. Moreover, the distance L between grains means the distance from the peak of a grain (the vertex of a convex part) to the peak of the grain adjacent to the said grain. From the distance L between grains, it can be understood how much grains exist per unit length, and the density of grains formed on the surface of the deposited film can also be understood.

  The film type that can be used as the vapor deposition film in this embodiment may be a transparent film or an opaque film, and is not particularly limited.

  The film types for forming a transparent film as a deposited film are aluminum oxide, zinc oxide, antimony oxide, indium oxide, calcium oxide, cadmium oxide, silver oxide, gold oxide, chromium oxide, silicon oxide, cobalt oxide, zirconium oxide, and oxide. Examples thereof include tin, titanium oxide, iron oxide, copper oxide, nickel oxide, platinum oxide, palladium oxide, bismuth oxide, magnesium oxide, manganese oxide, molybdenum oxide, vanadium oxide, and barium oxide. An ITO film or the like can also be used as the vapor deposition film 4.

  On the other hand, examples of the film type used as the vapor deposition film for forming the opaque film include aluminum and silicon, and all metals can be used as the film type.

  In this embodiment, a silicon oxide film is the most preferable material from the viewpoints of ease of manufacture and versatility of use.

  Since the film thickness of the vapor deposition film 4 is the same as the description regarding the silicon oxide film in the embodiment of the invention described in claim 1, the description is omitted here.

  In the present invention, the deposited film is formed by the plasma CVD method. This is because the film formed with the vapor deposition film by the plasma CVD method has flexibility as a whole and can be applied not only to various applications but also because the productivity is high, the utility value of the gas barrier film can be improved. It is.

  In order to manufacture the gas barrier film according to the invention of claim 3, it is necessary to adjust the distance L between the grains 4a formed on the surface of the vapor deposition film 4, and for this purpose, the vapor deposition film forming material has energy. It is preferable to increase the input power in order to reach the surface of the base film 1 and form a structurally stable and dense film.

  In addition, when the deposited film is formed, it is possible to obtain a structurally stable and dense film by making the deposited molecules easily migrate on the surface of the base film 1. It is also preferable to increase the temperature.

  Since the base film 1 and the composite polymer layer 3 are the same as those described for the base film 1 and the composite polymer layer 3 according to claim 1, description thereof is omitted here.

  The gas barrier film according to the invention of claim 3 has a high barrier property against oxygen, water vapor and the like, and has a barrier property against gas such as oxygen and water vapor even under humid conditions, although it is a thin gas barrier film. It has the advantage that it does not decrease. Using the gas barrier film of the present invention or the laminate material using the gas barrier film, a packaging container suitable for filling bags with various forms can be manufactured.

  The packaging container obtained by using the gas barrier film of the present invention or the laminate using the gas barrier film has not only high barrier properties against oxygen, water vapor, etc., but also transparency, heat resistance, impact resistance, etc. Excellent, suitable for post-processing such as laminating, printing, bag making, etc., for example, chemicals such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other various articles It is excellent in filling packaging suitability, storage suitability, and the like.

  The gas barrier film according to the invention of claim 3 has a high barrier property against oxygen, water vapor and the like, and has a barrier property against gas such as oxygen and water vapor even under humid conditions, although it is a thin gas barrier film. Since it has the advantage that it does not decrease, it is useful not only for packaging materials such as food, tobacco and toiletries, but also for gas barrier films for film liquid crystal displays, gas barrier films for film organic EL displays, or gas barriers for solar cells. It is used for applications such as membranes.

(Third embodiment: Embodiment of the invention described in claim 5)
Next, an embodiment of the invention described in claim 5 will be described with reference to FIG. This embodiment is composed of a base film 1, a silicon oxide film 5, and a composite polymer layer 3 in the same manner as the gas barrier film of the invention described in claim 1, wherein the silicon oxide film 5 is formed by an electron spin resonance method. (ESR method) It has an E ′ center observed by measurement.

  First, the E ′ center will be described.

  The E ′ center is an unpaired electron, and the following [Chemical Formula 1] is a structural formula of a silicon atom having an E ′ center, that is, an unpaired electron.

  Ordinary silicon atoms have four arms for covalently bonding to other atoms, and therefore silicon atoms in a normal silicon oxide film are bonded to four adjacent oxygen atoms. However, the E ′ center, that is, the silicon atom having unpaired electrons, has three arms bonded to oxygen atoms out of the four arms, but the fourth arm exists as unpaired electrons, and oxygen It does not form a covalent bond with the atom. For this reason, a silicon oxide film composed of silicon atoms having an E ′ center has a structure in which the film is densely distorted. Therefore, since the silicon oxide film having the E ′ center has no single bond between the silicon atom and the oxygen atom, other silicon atoms and oxygen atoms can enter the portion, so that the crystal is clogged as compared with the normal crystal structure. Thus, a gas barrier film excellent in gas barrier is formed.

Here, in the present invention, the density of the E ′ center observed by the electron spin resonance (ESR) measurement is 5 × 10 ¹⁵ spins / cm ³ or more. This is because a silicon oxide film having an E ′ center density of 5 × 10 ¹⁵ spins / cm ³ or more surely takes a structure in which the film structure is densely distorted, and the silicon oxide film is a layer having a high barrier property. It is because it forms. The density of the E ′ center is preferably 1 × 10 ¹⁸ spins / cm ³ or less. This is because as the density of the E ′ center increases, the number of bonds between oxygen atoms decreases, and when it exceeds 1 × 10 ¹⁸ spins / cm ³ , it becomes difficult to form a crystal film.

  Next, the electron spin resonance method (ESR method) will be described.

  Substances that have unpaired electrons, such as radicals and transition metal atom ions, and exhibit magnetism by their spin are called paramagnetic substances, and substances that do not have unpaired electrons are called diamagnetic substances. Here, the electron spin resonance method (ESR method) is an absorption spectrum method using an unpaired electron of a paramagnetic substance. By this electron spin resonance method (ESR method), the electronic state of the silicon oxide film and it are placed. You can get information about your environment.

  When measuring the density of the E ′ center of the silicon oxide film, any of conventionally known electron spin resonance methods can be used, and the measuring apparatus and the like are not particularly limited.

  Since the film thickness of the vapor deposition film 5 is the same as the description regarding the silicon oxide film in the embodiment of the invention described in claim 1, the description is omitted here.

  In the present invention, the silicon oxide film is formed by the plasma CVD method. This is because the film formed with the vapor deposition film by the plasma CVD method has flexibility as a whole and can be applied not only to various applications but also because the productivity is high, the utility value of the gas barrier film can be improved. It is.

  In order to manufacture the gas barrier film according to the invention of claim 5, it is necessary to adjust the E ′ center density of the silicon oxide film 5, but when the silicon oxide film 5 is formed by the plasma CVD method, plasma is generated. It is preferable to increase the input power in the means. Since energy is given to the material for forming the silicon oxide film by increasing the input power, the raw material molecules can be brought into a very active state, the probability that the bond is broken increases, and the E ′ center ( This is because a film having unpaired electrons) can be obtained.

  It is also preferable to reduce the pressure during film formation. By reducing the pressure at the time of film formation, the probability that atoms (silicon atoms and oxygen atoms) that form the silicon oxide film collide with each other can be lowered, and thus a film having an E ′ center (unpaired electron) is obtained. Because it can.

  In this embodiment, the transparency of the silicon oxide film 5 is the same as that described in the description of the first embodiment, and thus the description thereof is omitted here.

  Since the film thickness of the silicon oxide film 5 is the same as that described for the silicon oxide film in the embodiment of the invention described in claim 1, the description is omitted here.

  Since the base film 1 and the composite polymer layer 3 are the same as those described for the base film 1 and the composite polymer layer 3 according to claim 1, description thereof is omitted here.

  The gas barrier film according to the invention of claim 5 has a high barrier property against oxygen, water vapor and the like, and has a barrier property against gas such as oxygen and water vapor even under humid conditions, although it is a thin gas barrier film. It has the advantage that it does not decrease.

The packaging container obtained using the gas barrier film of the present invention has not only high barrier properties against oxygen, water vapor, etc., but also excellent transparency, heat resistance, impact resistance, etc., laminating, printing, bag making It has post-processing suitability such as processing, for example, foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, chemicals such as toothpastes, adhesives, adhesives, etc. It is.

  The gas barrier film according to the invention of claim 5 has a high barrier property against oxygen, water vapor and the like, and has a barrier property against gas such as oxygen and water vapor even under humid conditions, although it is a thin gas barrier film. Since it has the advantage that it does not decrease, it is useful not only for packaging materials such as food, tobacco and toiletries, but also for gas barrier films for film liquid crystal displays, gas barrier films for film organic EL displays, or gas barriers for solar cells. It is used for applications such as membranes.

(Fourth embodiment: Embodiment of the invention described in claim 6)
Next, an embodiment of the invention described in claim 6 will be described with reference to FIG. This embodiment is composed of the base film 1, the silicon oxide film 6 and the composite polymer layer 3 in the same manner as the gas barrier film of the invention described in claim 1, provided that the silicon oxide film 6 is 2341 ± 4 cm ^{−. 1} is characterized by having an IR absorption peak based on the stretching vibration of CO molecules.

If there is an IR absorption peak based on the stretching vibration of CO molecules at 2341 ± 4 cm ⁻¹ , the reason why the gas barrier property is improved is not clear, but is considered as follows. That is, the presence of the IR absorption peak is considered that CO molecules are physically adsorbed in the silicon oxide film, that is, CO molecules are taken into the silicon oxide film.

  Conventional silicon oxide films are composed of bonds of silicon atoms and oxygen atoms, and there are many voids between silicon atoms and oxygen atoms. However, in the silicon oxide film of this embodiment, CO molecules are taken into the film in a gas state, and the gap between the silicon atoms and the oxygen atoms is clogged with the CO molecules. It is considered that there are fewer voids than the silicon oxide film, and as a result, excellent gas barrier properties are exhibited.

Further, when considered as described above, the CO molecules physically adsorbed in the silicon oxide film of this embodiment, that is, the CO molecules taken into the film are formed when the silicon oxide film is formed by the plasma CVD method. Further, it is considered that the organic silicon compound used as a raw material is formed by being decomposed (oxidized). The CO molecules physically adsorbed in the silicon oxide film are formed simultaneously with the formation of the silicon oxide film. If the formed silicon oxide film has many voids, the physical properties of the CO molecules Adsorption does not occur, and it can be naturally predicted that the gas is released as it is from the membrane into the air. On the other hand, in the silicon oxide film of this embodiment, the silicon oxide film has an IR absorption peak based on the stretching vibration of CO molecules at 2341 ± 4 cm ^−1. It is apparent that the gaseous CO molecules formed as so-called by-products are physically adsorbed. This can serve as a basis for thinking that the silicon oxide film of this embodiment has a structure that is so dense that the CO molecular gas cannot diffuse out of the film.

When considered as described above, the peak of IR absorption based on the stretching vibration of the CO molecule usually appears at 2341 cm ⁻¹ , but in the present invention, considering the resolution of the apparatus when performing IR measurement, 2341 ± 4 cm ⁻¹ .

Here, in IR measurement, in order to have an IR absorption peak based on the stretching vibration of CO molecules at 2341 ± 4 cm ⁻¹ , the input power in the plasma generating means when the silicon oxide film is formed by the plasma CVD method. Should be increased. This is because bond breaking in the molecule of the organosilicon compound used as a raw material for the silicon oxide film can be promoted, and CO molecules are easily formed. In addition, CO molecules may be easily formed by adjusting the flow rate ratio between the organic silicon compound as a raw material and oxygen.

Further, in the IR measurement, the intensity of the peak of IR absorption based on the stretching vibration of CO molecules appearing in the portion of 2341 ± 4 cm ⁻¹ is preferably 0.005 to 0.3 in terms of absorbance (Absorbance). This is because if the absorbance within the above range can be confirmed, it is clear that gaseous CO molecules are physically adsorbed in the silicon oxide film.

  In this embodiment, IR absorption is evaluated by measuring with an IR spectrophotometer for IR measurement. Preferably, an infrared absorption spectrum is measured by attaching an ATR (multiple reflection) measuring device to the infrared spectrophotometer. At this time, it is preferable to use a germanium crystal for the prism and measure at an incident angle of 45 degrees.

  Since the film thickness of the silicon oxide film 6 is the same as that described for the silicon oxide film in the embodiment of the invention described in claim 1, the description is omitted here.

  In this embodiment, the transparency of the silicon oxide film 6 is the same as that described in the description of the first embodiment, and thus the description thereof is omitted here.

  Since the base film 1 and the composite polymer layer 3 are the same as those described for the base film 1 and the composite polymer layer 3 according to claim 1, description thereof is omitted here.

  The gas barrier film according to the invention described in claim 6 has a high barrier property against oxygen, water vapor, etc., while being a thin gas barrier film, and has a barrier property against gas such as oxygen, water vapor, etc. even under humid conditions. It has the advantage that it does not decrease.

  The packaging container obtained by using the gas barrier film of the present invention or the laminate using the gas barrier film has not only high barrier properties against oxygen, water vapor, etc., but also transparency, heat resistance, impact resistance, etc. Excellent, suitable for post-processing such as laminating, printing, bag making, etc., for example, chemicals such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other various articles It is excellent in filling packaging suitability, storage suitability, and the like.

  The gas barrier film according to the invention described in claim 6 has a high barrier property against oxygen, water vapor, etc., while being a thin gas barrier film, and has a barrier property against gas such as oxygen, water vapor, etc. even under humid conditions. Since it has the advantage that it does not decrease, it is useful not only for packaging materials such as food, tobacco and toiletries, but also for gas barrier films for film liquid crystal displays, gas barrier films for film organic EL displays, or gas barriers for solar cells. It is used for applications such as membranes.

(Combination of Embodiments 1 to 4)
The scope of the present invention includes a gas barrier film using a vapor deposition layer having two or more types of characteristics among the characteristics of the vapor deposition layer shown in the first to fourth embodiments.

(Production method according to claim 9)
The gas barrier film of the present invention uses, as a raw material gas, a gas containing an organic silicon compound that does not have a carbon-silicon bond in the molecule and a gas containing oxygen atoms, and a flow rate ratio between the gas of the organic silicon compound and the gas containing oxygen atoms. Is introduced into the reaction chamber in the range of 1: 3 to 1:50, and a process of forming a silicon oxide film on the base film placed in the reaction chamber by plasma CVD, and after the film formation, on the silicon oxide film Is obtained by polycondensing a composition containing an alkoxysilane, a silane coupling agent and polyvinyl alcohol in the presence of a sol-gel method catalyst, a mineral acid, water, and an organic solvent. A process of applying a coating liquid containing the composite polymer of the composition, and then heat-treating the coating film of the coating liquid at a temperature of 120 ° C. or higher and a melting point of the base film or lower. Forming a composite polymer layer of the composition on the silicon oxide film can be obtained by the method for producing a gas barrier film characterized by. Hereinafter, (a) a process for forming a deposited film and (b) a process for forming a composite polymer layer will be described in order.

(A) Film formation process of vapor deposition film The vapor deposition film supplies a mixture gas of an organosilicon compound gas and oxygen gas at a predetermined flow rate into a reaction chamber of a plasma CVD apparatus, and direct current power or low frequency to high frequency to an electrode. The plasma is generated by applying power having a constant frequency within the range of the above, and the organosilicon compound gas is formed on the base film by reacting with the oxygen-containing gas, particularly oxygen gas, in the plasma. . The type of the plasma CVD apparatus used is not particularly limited, and various types of plasma CVD apparatuses can be used. Usually, an apparatus capable of continuous film formation, which can use a long polymer resin film as a base film and continuously form a deposited film while transporting it, is preferably used. The temperature of the base film during the preferred film formation by this plasma CVD method is in the range of -20 to 100 ° C, preferably in the range of -10 to 30 ° C.

  Next, when a gas containing an organosilicon compound gas and an oxygen gas is used as a source gas and the flow rate ratio between the organosilicon compound gas and the oxygen gas is 1, the organosilicon compound gas is within a range of 3 to 50, Preferably it shall be in the range of 3-10.

  And by increasing the input power per unit area in the plasma generating means of the plasma CVD apparatus, or by forming a plasma confinement space with a magnet or the like, by increasing the reactivity of the gas containing the organosilicon compound gas and oxygen gas, The effect of plasma generation is higher.

  In the present invention, among the raw material gases, the organosilicon compound gas includes hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane (TMDSO), vinyltrimethoxysilane, vinyl. Trimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, tetraethoxysilane (TEOS), dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexamethyldisilane are preferably used. In addition, one or two or more conventionally known compounds such as tetramethyldisiloxane and normal trimethoxytrimethoxysilane can be used.

However, in the present invention, an organosilicon compound having no carbon-silicon bond in the molecule can be preferably used for the purpose of forming a SiO ₂ -like film. Specific examples include tetramethoxysilane (TMOS), methyltrimethoxysilane, methyldimethoxysilane, tetraethoxysilane (TEOS), methyltriethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and methyldiethoxysilane. Among these, tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) having no carbon-silicon bond in the molecule are preferably used.

Examples of the gas containing oxygen atoms include N ₂ O, oxygen, CO, CO _2, etc. Among them, oxygen gas can be preferably used.

  In this invention, it is preferable to heat-process the obtained vapor deposition film at the temperature of 50-200 degreeC. In this way, by further heat-treating the obtained silicon oxide film, a silicon oxide film with better gas barrier properties can be obtained.

In the present invention, when this heat treatment is performed, in the case of a silicon oxide film having an IR absorption peak based on the stretching vibration of CO molecules at 2341 ± 4 cm ⁻¹ before the heat treatment (in the case of the fourth embodiment). Is preferably performed until the peak of IR absorption based on the stretching vibration of the CO molecule disappears.

As described above, heating until 2341 ± 4 cm ⁻¹ has no IR absorption peak due to the stretching vibration of the CO molecule increases the vibration of the molecular bond by giving thermal energy to the film, so that the CO molecule can be transmitted. This is probably because a space is formed, the captured CO molecules are desorbed, and then the bonds become tighter as much as the CO molecules are released, thereby forming a denser film. Therefore, it is considered that the gas barrier property is further improved by heating until the above peak disappears. Here, “the peak disappears” means that the state is below the detection limit of the analyzer.

  Thus, the specific heating time until the above peak disappears greatly varies depending on the heat treatment temperature, but if it is 5 minutes or more, heating for about 30 minutes or more is required. If it is 70 degreeC or more, the heating for 5 minutes or more is required. In addition, you may perform this heat processing after formation of the composite polymer layer mentioned later.

(Formation process of composite polymer layer)
A composite polymer layer is formed on the deposited film as follows.

  First, the said alkoxysilane, a silane coupling agent, PVA, a sol-gel method catalyst, a mineral acid, water, an organic solvent, and a metal alkoxide as needed are mixed and a coating liquid is prepared. In this coating solution, the polycondensation reaction gradually proceeds.

  Next, the coating liquid is applied onto the silicon oxide film formed on the base film and dried. By the drying, the polycondensation of the alkoxysilane, metal alkoxide, silane coupling agent, and PVA further proceeds to form a composite polymer layer. Preferably, the above coating and drying operations are repeated to laminate a plurality of composite polymer layers. Finally, when the film coated with the coating solution is heated at 120 ° C. or higher and below the melting point of the base film, preferably at a temperature in the range of 150 to 200 ° C. for 30 seconds to 10 minutes, the present invention The gas barrier film is obtained. The gas barrier film of the present invention thus obtained is subjected to an acetalization treatment as necessary. Specifically, the film on which the composite polymer layer is laminated is immersed in an aldehyde solution containing an acid. By performing acetalization treatment using formaldehyde, acetaldehyde, butyraldehyde, etc. as the aldehyde, the unreacted hydroxyl group caused by PVA present in a minute amount in the composite polymer reacts with the aldehyde to be acetalized, and the water resistance ( Moisture resistance) is further improved.

The alkoxysilane used in the present invention is represented by Si (OR ¹ ) ₄ , and R ¹ is a lower alkyl group. Specifically, Si (O—CH ₃ ) ₄ , Si (O—C ₂ H ₅ ) ₄ or the like is used. A mixture of these alkoxysilanes may be used.

Moreover, metal alkoxides, such as a zirconium alkoxide and a titanium alkoxide, can be used as a component of a composition with the said alkoxysilane as needed. The zirconium alkoxide is represented by Zr (OR ² ) ₄ and R ² is a lower alkyl group. Specifically, Zr (O—CH ₃ ) ₄ , Zr (O—C ₂ H ₅ ) ₄ , Zr (O—isoC ₃ H ₇ ) ₄ , Zr (O—C ₄ H ₉ ) ₄ are used as metal alkoxides. Etc. can be used. Here, two or more kinds of these metal alkoxides may be mixed and used as a component of the composition. By using zirconium alkoxide as a component of the composition, the toughness and heat resistance of the obtained gas barrier film are improved. The amount 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 the 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 is easily peeled from the silicon oxide film. Next, the titanium alkoxide is represented by Ti (OR ³ ) ₄ and R ³ is a lower alkyl group. Specifically, Ti (O—CH ₃ ) ₄ , Ti (O—C ₂ H ₅ ) ₄ , Ti (O—C ₃ H ₇ ) ₄ , Ti (O—C ₄ H ₉ ) _{4 and the} like are used as a composition. It can be used as a component. Two or more of these alkoxide silanes may be used as a component of the composition. By using titanium alkoxide, the thermal conductivity of the resulting coating is lowered, and the heat resistance of the base film is significantly improved. The amount 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 the alkoxysilane. When the amount exceeds 5 parts by weight, the brittleness of the composite polymer formed becomes large, and the composite polymer from the silicon oxide film is easily peeled off.

  As a silane coupling agent used as a component of the composition together with the alkoxide, a known organic reactive group-containing organoalkoxysilane can be used. In particular, an organoalkoxysilane having an epoxy group is suitable. Examples of the organoalkoxysilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. You may mix and use 2 or more types of such a silane coupling agent. The amount of the silane coupling agent used is in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. If an amount of more than 20 parts by weight is used, the insulating property and workability of the formed composite polymer layer are lowered.

  In the present invention, polyvinyl alcohol (PVA) is contained in the composition constituting the composite polymer. By adding PVA, the gas barrier properties of the resulting polymer are significantly improved. The content of PVA is in the range of 50 to 200 parts by weight, preferably about 100 parts by weight, with respect to 100 parts by weight of the total amount of the alkoxysilane and metal alkoxide. When the content of PVA exceeds 200 parts by weight with respect to 100 parts by weight of the total amount of the alkoxysilane and metal alkoxide, the brittleness of the composite polymer increases, and the water resistance of the resulting composite polymer layer decreases, resulting in 50 weights. If it is less than%, the gas barrier property is lowered.

  In the present invention, as the sol-gel catalyst used, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Examples thereof include N, N-dimethylbenzylamine, tripropylamine, tributylamine, and tripentylamine, and N, N-dibutylbenzylamine 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 alkoxylane, metal alkoxide, and silane coupling agent. The mineral acid used in the present invention is used not only as a catalyst for the sol-gel method but also as an acetalization catalyst (mainly a hydrolysis catalyst) described later. As the mineral acid, sulfuric acid, hydrochloric acid, nitric acid and the like are used. The amount of mineral acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of alkoxysilane, metal alkoxide, and alkoxide content of the silane coupling agent (silicate portion). It is.

  In the present invention, 0.8 to 2 mol of water is used with respect to the total molar amount of the alkoxysilane and metal alkoxide. When the amount of water exceeds 2 mol, the composite polymer containing the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles crosslink three-dimensionally to form a porous polymer with low density. The composite polymer layer composed of the porous polymer does not provide a gas barrier film having a high gas barrier property. On the other hand, when the amount of water is less than 0.8 mol, the hydrolysis reaction hardly proceeds.

  As the organic solvent used in the present invention, the amount of the solvent in which ethyl alcohol, isopropyl alcohol, butyl alcohol or the like is used is the above-mentioned normal alkoxysilane, metal alkoxide, silane coupling agent, PVA, mineral acid, and sol- It is 30 to 100 parts by weight per 100 parts by weight of the total amount of the gel method catalyst.

  In the method of the present invention, the alkoxysilane and the metal alkoxide are hydrolyzed by the added water. Next, protons are taken from the generated hydroxyl groups by the action of the sol-gel method catalyst, and hydrolyzed products undergo dehydration polycondensation. At this time, the silane coupling agent is simultaneously hydrolyzed and the alkoxy group becomes a hydroxyl group. The opening of the epoxy group also occurs due to the action of the catalyst, resulting in a hydroxyl group. A polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds. Furthermore, since PVA exists in the reaction system, a reaction with the hydroxyl group of PVA also occurs. The resulting polycondensate is a composite polymer containing an inorganic part composed of a bond such as Si-O-Si, Si-O-Zr, Si-O-Ti, and an organic part derived from a silane coupling agent. . In the above reaction, for example, a linear polymer having a partial structural formula represented by the formula (II) and further having a portion derived from a silane coupling agent is first formed. This polymer has a form in which an OR group (an alkoxy group such as an ethoxy group) is branched from a linear polymer. This OR group is hydrolyzed to become an OH group using the existing mineral acid as a catalyst, which undergoes a polycondensation reaction with the PVA represented by the formula (I) to form the formula (III) having a Si—O—Si bond. It is believed that the composite polymer shown results. In the polycondensation reaction, the OH group is first deprotonated by the action of a sol-gel catalyst (hydrochloric acid catalyst), and then polycondensation proceeds.

  The above reaction proceeds at room temperature, and the viscosity of the coating solution increases during the preparation of the coating solution. When this coating solution is applied to the silicon oxide film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, the polycondensation is completed and a composite polymer layer is formed on the silicon oxide film. When a plurality of composite polymer layers are stacked, the composite polymers between the layers are also condensed to form a space between the layers.

  In the present invention, the amount of water added is adjusted to 0.8 mol to 2 mol, preferably 1.5 mol, with respect to 1 mol of the total molar amount of alkoxysilane or alkoxysilane and metal alkoxide. Therefore, the linear polymer is formed. Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part. Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride resin or PVA), and a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Because of its high rigidity, it exhibits good gas barrier properties. The Si—O—CH bond of the polymer represented by the formula (III) is the same as the stable bond state formed by acetylation or formalization of PVA.

  The composite polymer layer thus obtained is excellent in water resistance, but can be further improved by further acetalizing treatment as described above. The composite polymer layer is obtained by polycondensing a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol on a silicon oxide film in the presence of a sol-gel method catalyst, a mineral acid, water, and an organic solvent. Then, a coating liquid containing a composite polymer of the composition consisting of a linear polymer as a main component is applied, and then the coating film of the coating liquid is at a temperature not lower than 120 ° C. and not higher than the melting point of the base film. It is formed by heat treatment.

  A heat-sealable resin layer may be provided on the composite polymer layer of the gas barrier film via an anchor coat agent layer or an adhesive layer.

As the anchor coating agent, for example, an organic titanium anchor coating agent such as alkyl titanate, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, or the like can be used. For the formation of the anchor coating agent layer, the above-mentioned anchor coating agent is coated by a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and the solvent, diluent, etc. are dried and removed. Can be done. The application amount of the anchor coating agent is preferably about 0.5 to 5 g / m ² (dry state).

Examples of the adhesive include polyurethane, polyester, polyamide, epoxy, poly (meth) acrylic, polyvinyl acetate, polyolefin, casein, wax, and ethylene- (meth) acrylic acid copolymer. It can be formed by using various types of laminating adhesives such as a solvent type, a water-based type, a solventless type, or a heat melting type mainly composed of a vehicle such as a coalescence or polybutadiene. The adhesive layer is formed by applying the above-mentioned adhesive by, for example, roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and drying and removing the solvent, diluent, and the like. Can do. The amount of the adhesive applied is preferably about 0.1 to 5 g / m ² (dry state).

  Examples of the heat-sealable resin include resins that can be melted by heat and fused to the composite polymer layer. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as acid, fumaric acid, and itaconic acid, a polyvinyl acetate resin, a poly (meth) acrylic resin, and a polyvinyl chloride resin can be used. The heat-sealable resin layer may be formed by directly applying a heat-sealable resin on the composite polymer layer, or may be formed by directly laminating a film made of the above heat-sealable resin on the composite polymer layer. good. The thickness of the heat-sealable resin layer can be set within a range of 5 to 300 μm, preferably 10 to 100 μm.

  Furthermore, a base material layer can be laminated on the composite polymer layer of the gas barrier film via an anchor coating agent layer / adhesive layer and a heat sealable resin layer to form a laminated material. When this laminated material is used as a constituent material of a packaging container, since the base material layer becomes a basic material, it has mechanical, physical properties, chemical properties, and other excellent properties. A tough and heat-resistant resin film or sheet can be used as the base material layer. Specifically, a polyester resin, a polyamide resin, a polyaramid resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin, a polyacetal resin, a tough resin such as a fluorine resin (uniaxial or biaxial) stretching or An unstretched film or sheet can be mentioned. The thickness of the base material layer is 5 to 100 μm, preferably about 10 to 50 μm.

  Further, for example, a desired printing pattern such as a character, a figure, a symbol, and a pattern may be subjected to surface printing or back printing by a normal printing method on the base material layer.

Furthermore, for example, various paper base materials can be used as the base material layer. Specifically, it is a paper base material that has formability, bending resistance, rigidity, etc., for example, a strong or small bleached or unbleached paper base material, or a pure white roll view, kraft paper, paperboard, processing A paper substrate such as paper can be used. As such a paper substrate, a substrate having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² can be used as the substrate layer.

  In addition, as the base material layer, the above-mentioned polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluororesin, etc. ) A stretched or unstretched film or sheet and the above-mentioned paper base material may be combined and used.

  Further, an anchor coat agent layer / adhesive layer and a heat seal agent layer layer are provided on the composite polymer layer of the gas barrier film, and the opposite side of the base film of the gas barrier film (the silicon oxide film and the composite polymer layer are not provided). A second base material layer and a second heat sealant layer may be provided on the side).

  Next, the production method of the gas barrier film will be specifically described with reference to examples. In Reference Examples and Examples, parts and% are expressed on a weight basis.

  First, the preparation of a coating solution to be applied on the silicon oxide film used in Examples 1 to 4 and Comparative Examples 1 to 4 described later will be described with reference examples 1 to 7.

[Reference Example 1: Preparation of coating liquid (A)]
25 g of ethyl silicate, 25 g of ethanol, 1.86 g of 2N hydrochloric acid and 1.51 g of water were mixed and stirred at 80 ° C. for 1 to 2 hours to obtain a mixed solution. At this time, the ratio of ethyl silicate to water in the mixed solution is 1 mol to 1.5 l. Next, 2.5 g of epoxysilane SH6040 (manufactured by Toray Dow Corning) was added to the mixed solution and stirred.

  Further, 17.4 g of an aqueous solution containing 10% of PVA polymerization degree 2000 (manufactured by Kuraray Co., Ltd.) was added, and when it became transparent after stirring for 1 to 2 hours, 0.1 g of NN dimethylbenzylamine 32 wt% ethanol solution was added. The mixture was stirred to obtain a coating liquid (A) containing a composite polymer whose main component was a linear polymer.

[Reference Example 2: Preparation of coating liquid (B)]
1 g of zirconium isopropoxide was added to the coating liquid of Reference Example 1 and stirred to obtain a coating liquid (B).

As the base film, a sheet-like biaxially stretched polyester film [trade name: Toyobo E5100, thickness: 12 μm] having a corona treatment on one side was prepared. As shown in FIG. 6, the base film 20 was mounted on the lower electrode 114 side in the chamber 102 of the plasma CVD apparatus 101. Next, the inside of the chamber 102 of the plasma CVD apparatus 101 was depressurized to an arrival vacuum of 3.0 × 10 ⁻⁵ Torr (4.0 × 10 ⁻³ Pa) by an oil rotary pump and a turbo molecular pump. Next, power having a frequency of 90 KHz (applied power 150 W) was applied to the lower electrode 114 from the high frequency power source 107. Then, 10 sccm of tetramethoxysilane (TMOS) gas (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-04) and 100 sccm of oxygen are introduced from a gas inlet 109 provided in the vicinity of the electrode in the chamber 102, and the vacuum pump 108 and the chamber By controlling the degree of opening and closing of the valve 113 between the film 102 and the substrate 102, the pressure inside the film forming chamber was kept at 0.25 Torr, and a silicon oxide film having a thickness of 50 nm was formed on the base film 20. Here, sccm is an abbreviation for “standard cubic centimeter per minute”.

  Next, the coating liquid (A) prepared in Reference Example 1 was applied on the silicon oxide film formed by a bar coater and dried at 150 ° C. for 10 minutes by a hot air dryer, and the coating composition having a thickness of 2.0 μm. The coating film of (A) was formed, and the gas barrier film of Example 1 was obtained.

  When forming the silicon oxide film, the silicon oxide film was formed in the same manner as in Example 1 except that only TMOS 10 sccm instead of TMOS gas and oxygen gas was introduced into the chamber as the source gas. The coating liquid (A) prepared in Reference Example 1 was applied and dried to obtain a gas barrier film of Example 2.

  A gas barrier film of Example 3 was obtained in the same manner as in Example 1 except that the coating liquid (A) was changed to the coating liquid (B) in Example 1.

  A gas barrier film of Example 4 was obtained in the same manner as in Example 2 except that the coating liquid (A) was changed to the coating liquid (B) in Example 2.

[Comparative Example 1]
When forming the silicon oxide film, instead of TMOS gas and oxygen gas, hexamethyldisiloxane (HMDSO) gas (product name: SH200, 0.65 Cst) 10 sccm and oxygen gas 5 sccm are used instead of TMOS gas and oxygen gas. A gas film of Comparative Example 1 was obtained in the same manner as in Example 1 except that was introduced into the chamber.

[Comparative Example 2]
The gas of Comparative Example 2 was prepared in the same manner as in Example 1 except that, when forming the silicon oxide film, HMDSO gas 10 sccm and oxygen gas 10 sccm were introduced into the chamber instead of TMOS gas and oxygen gas as source gases. A film was obtained.

[Comparative Example 3]
A gas barrier film of Comparative Example 3 was obtained in the same manner as in Example 1 except that the coating liquid (A) was not applied to the silicon oxide film.

[Evaluation methods]
The obtained gas barrier film was subjected to measurement of oxygen gas permeability and water vapor permeability to evaluate gas barrier properties. The oxygen gas permeability was measured under conditions of 23 ° C., dry (0% RH) and 90% RH using an oxygen gas permeability measuring device (manufactured by MOSCON, OX-TRAN 2-20). Further, the water vapor transmission rate was measured under the conditions of 37.8 ° C. and 100% RH using a water vapor transmission rate measuring device (manufactured by MOSCON, PERMATRAN-W3 / 31).

  The component ratio (Si: O: C) of the silicon oxide film was measured by an ESCA apparatus (manufactured by VG Scientific, UK, ESCA LAB220i-XL). At that time, as an X-ray source, an Ag-3d-5 / 2 peak intensity, a monochrome AlX ray source having 300 K to 1 Mcps, and a slit having a diameter of about 1 mmφ were used. The measurement was performed with the detector set on the normal line with respect to the sample surface subjected to the measurement, and appropriate charge correction was performed. The analysis after the measurement uses the software Eclipse version 2.1 (manufactured by VG Scientific, UK) attached to the ESCA apparatus, and corresponds to the binding energy (Binding energy) of Si: 2p, C: 1s, and O: 1s. It was performed using the peak. At this time, the background of Shirley is removed for each peak, the sensitivity coefficient of each element is corrected for the peak area (Si = 0.817, O = 2.930 for C = 1), and the number of atoms The ratio was determined. About the obtained atomic ratio, the number of Si atoms was set to 100, and the number of atoms of O and C which are other components was calculated and evaluated as a component ratio.

  For IR measurement, a Fourier transform infrared spectrophotometer equipped with an ATR (multiple reflection) measuring device (manufactured by JASCO, ATR-300 / H) using a silicon oxide film before application of the coating solution as a sample (Japan) Spectroscopic, Herschel FT / IR-610). The infrared absorption spectrum was measured using a germanium crystal as a prism at an incident angle of 45 degrees.

  The refractive index of the silicon oxide film is obtained by measuring the transmittance and the reflectance with an optical spectrometer (manufactured by Shimadzu Corporation, UV-3100PC) using the silicon oxide film before coating the coating liquid as a sample. From the measurement results of the reflectance, the refractive index at 633 nm was obtained and evaluated using an optical interference method.

  The measurement and evaluation of the distance between grains was performed as follows. The silicon oxide film before application of the coating solution was used as a sample, and first, the silicon oxide film surface was treated with an ammonium fluoride aqueous solution. This treatment utilizes the property that the boundary is dissolved by the aqueous ammonium fluoride solution, but the grains are difficult to dissolve. By performing this treatment, the grains formed on the surface of the silicon oxide film are used. Observation became possible. An arbitrary surface of a silicon oxide film having a grain was observed using an atomic force microscope (Nano Scope III manufactured by Digital Instruments), and the distance between peaks of two adjacent grains having substantially the same peak height was measured.

  Using the silicon oxide film before the coating liquid was applied as a sample, the E ′ center density of this silicon oxide film was measured by an electron spin resonance method (ESR method). The apparatus, measurement conditions, and analysis method used for the measurement were as follows.

(measuring device)
Main device: ESR350E (manufactured by BRUCKER)
Attached equipment: HP5351B microwave frequency counter (manufactured by HEWLETT PACKERD), ER035M Gauss meter (manufactured by BRUKER, ESR910), and cryostat (manufactured by OXFORD)

(Measurement condition)
Measurement temperature: Room temperature (23 ° C)
Magnetic field sweep range: 331.5-341.5 mT
Modulation: 100KHz, 0.2mT
Microwave: 9.43 GHz, 0.1 mW
Sweep time: 83.886 sec × 4 times Time constant: 327.68 msec
Data points: 1024 points cavity: TM _10, cylindrical

(analysis method)
A signal attributed to the E ′ center was observed in the silicon oxide film in the vicinity of g = 2.0003. The ESR spectrum is usually used as a differential curve, and an absorption curve is obtained by one-time differentiation, and a signal intensity (area intensity) is obtained by two-time differentiation. The number of spins represents the number of unpaired electrons, and is a value obtained from signal intensity using a polyethylene film ion-implanted as a secondary standard sample. As the primary standard sample, sulfuric acid cylinder pentahydrate was used. A value obtained by normalizing the number of E ′ center spins by the film thickness and measurement area is obtained as E ′ center density (spins / cm ³ ). The detection limit of the E ′ center in the above measuring apparatus was 5 × 10 ¹⁵ spins / cm ³ .

  The results of the above evaluation are shown in Table 1.

Although the gas barrier film of Example 1 is a thin film with a silicon oxide film of 50 nm and a coating liquid coating film thickness of 2.0 μm, an oxygen permeability of 0. It has an oxygen permeability of 0.3 cc / m ² / day / atm under the conditions of ² cc / m ² / day / atm and 90% RH, and the water vapor permeability is 0.8 cc / m ² / day / atm. It was found that it has a high gas barrier property. At this time, the Si—O—Si absorption peak position indicating IR absorption based on the Si—O—Si stretching vibration is 1063 cm ⁻¹ , the refractive index is 1.47, and the E ′ center density is 2 3 × 10 ¹⁶ spins / cm ³ and the distance between grains was ²¹ nm.

Although the gas barrier film of Example 2 is a thin film with a silicon oxide film of 50 nm and a coating liquid coating film thickness of 2.0 μm, an oxygen permeability of 0. It has an oxygen permeability of 0.4 cc / m ² / day / atm under the conditions of ² cc / m ² / day / atm and 90% RH, and the water vapor permeability is 0.8 cc / m ² / day / atm. It was found that it has a high gas barrier property. At this time, the Si—O—Si absorption peak position indicating IR absorption based on the Si—O—Si stretching vibration is 1060 cm ⁻¹ , the refractive index is 1.47, and the E ′ center density is 2 3 × 10 ¹⁶ spins / cm ³ and the distance between grains was 22 nm.

Although the gas barrier film of Example 3 is a thin film having a silicon oxide film thickness of 50 nm and a coating liquid coating film thickness of 2.0 μm, an oxygen permeability of 0. It has an oxygen permeability of 0.3 cc / m ² / day / atm under the conditions of ² cc / m ² / day / atm and 90% RH, and the water vapor permeability is 0.7 cc / m ² / day / atm. It was found that it has a high gas barrier property. At this time, the Si—O—Si absorption peak position indicating IR absorption based on the Si—O—Si stretching vibration is 1063 cm ⁻¹ , the refractive index is 1.47, and the E ′ center density is 2 3 × 10 ¹⁶ spins / cm ³ and the distance between grains was ²¹ nm.

Although the gas barrier film of Example 4 is a thin film having a silicon oxide film thickness of 50 nm and a coating liquid coating film thickness of 2.0 μm, an oxygen permeability of 0. ^{3cc / m 2 / day / atm} , under conditions of 90% RH have an oxygen permeability ^{0.3cc / m 2 / day / atm} , moreover, the water vapor transmission rate is at 0.7cc / m ² / day / atm It was found that it has a high gas barrier property. At this time, the Si—O—Si absorption peak position indicating IR absorption based on the Si—O—Si stretching vibration is 1060 cm ⁻¹ , the refractive index is 1.47, and the E ′ center density is 2 3 × 10 ¹⁶ spins / cm ³ and the distance between grains was 22 nm.

The gas barrier film of Comparative Example 1, a silicon oxide film, the oxygen permeability under conditions of ^{RH 0% 1.2cc / m 2 /} day / atm, under conditions of 90% RH oxygen permeability 1.4 cc / m ² The water vapor permeability was 1.3 cc / m ² / day / atm, and the gas barrier was found to be lower than that of the gas barrier films of Examples 1 to 4. At this time, the Si—O—Si absorption peak position showing IR absorption based on the Si—O—Si stretching vibration was 1066 cm ⁻¹ and the refractive index was 1.42. E ′ center density was not detected. It was found that the distance between grains was 90 nm, which was larger than that of Examples 1 to 4.

The gas barrier film of Comparative Example 2, silicon oxide film, the oxygen permeability under conditions of ^{RH 0% 1.5cc / m 2 /} day / atm, under conditions of 90% RH oxygen permeability 1.7 cc / m ² The water vapor permeability was 1.4 cc / m ² / day / atm, and it was found that the gas barrier was lower than the gas barrier films of Examples 1 to 4. At this time, the Si—O—Si absorption peak position showing IR absorption based on the Si—O—Si stretching vibration was 1050 cm ⁻¹ and the refractive index was 1.52. E ′ center density was not detected. It was found that the distance between grains was 61 nm, which was larger than that of Examples 1 to 4.

Regarding the gas barrier film of Comparative Example 3, the silicon oxide film has an oxygen permeability of 1.8 cc / m ² / day / atm under the condition of 0% RH, and an oxygen permeability of 1.8 cc / day under the condition of 90% RH. Both were high with m ² / day / atm, and the water vapor permeability was as high as 1.5 cc / m ² / day / atm, indicating that the gas barrier was low compared to the gas barrier films of Examples 1 to 4. At this time, the Si—O—Si absorption peak position showing IR absorption based on the Si—O—Si stretching vibration was 1063 cm ⁻¹ and the refractive index was 1.47. The E ′ center density was 2.3 × 10 ¹⁶ .

  Although the gas barrier film of the present invention is a thin gas barrier film, it has a high barrier property against oxygen, water vapor and the like, and the barrier property against gases such as oxygen and water vapor does not deteriorate even under humid conditions. Since it has advantages, for example, chemical products such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, etc., miscellaneous goods, tobacco, packaging of products in the field of toiletries, gas barrier films for film liquid crystal displays, films It is used for applications such as a gas barrier film for organic EL displays or a gas barrier film for solar cells.

It is a schematic sectional drawing of the 1st embodiment of the gas barrier film of this invention. It is a schematic sectional drawing of the 2nd embodiment of the gas barrier film of this invention. It is an enlarged view which shows the grain in the 2nd embodiment of the gas barrier film shown in FIG. It is a schematic sectional drawing of the 3rd embodiment of the gas barrier film of this invention. It is a schematic sectional drawing of the 4th embodiment of the gas barrier film of this invention. It is a block diagram which shows an example of plasma CVDC4A.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base film 2 Silicon oxide film 3 Composite polymer layer 4 Deposition film 5 Silicon oxide film 6 Silicon oxide film 20 Base film 101 Plasma CVD apparatus 102 Chamber 107 High frequency power supply 108 Vacuum pump 109 Gas inlet 112 Source gas 113 Valve 114 Lower part electrode

Claims (14)

A substrate film, and a silicon oxide film formed on one or both surfaces of the substrate film by a plasma CVD method. The silicon oxide film has 170 to 200 oxygen atoms and 100 carbon atoms with respect to 100 silicon atoms. It has a component ratio of several 30 or less, and further has IR absorption based on Si—O—Si stretching vibration between 1055 and 1065 cm ⁻¹ , and an alkoxysilane and a silane coupling agent on the silicon oxide film And a gas barrier film obtained by laminating at least one composite polymer layer, the main component of which is a linear polymer, obtained by polycondensing a composition containing polyvinyl alcohol by a sol-gel method.   The gas barrier film according to claim 1, wherein the silicon oxide film has a refractive index of 1.45 to 1.48.   A base film, and a vapor deposition film formed on one surface or both surfaces of the base film by a plasma CVD method and having grains on the surface with a spacing of 5 to 40 nm, and alkoxysilane on the vapor deposition film, A gas barrier characterized by laminating at least one composite polymer layer comprising a linear polymer as a main component, obtained by polycondensation of a composition containing a silane coupling agent and polyvinyl alcohol by a sol-gel method. the film.   The gas barrier film according to claim 3, wherein the deposited film is a silicon oxide film. A base film and an E ′ center formed by plasma CVD on one or both sides of the base film and observed by an electron spin resonance method, and the density of the E ′ center is 5 × 10 ¹⁵ spins / cm ^A main component obtained by polycondensation of a composition containing an alkoxysilane, a silane coupling agent and polyvinyl alcohol on the silicon oxide film by a sol-gel method. A gas barrier film, wherein at least one composite polymer layer comprising a linear polymer is laminated. A substrate film and a silicon oxide film formed by plasma CVD on one or both surfaces of the substrate film, and the silicon oxide film absorbs IR at 2341 ± 4 cm ⁻¹ based on stretching vibration of CO molecules. It has a peak and is obtained by polycondensation of a composition containing alkoxysilane, a silane coupling agent and polyvinyl alcohol on the silicon oxide film by a sol-gel method. A gas barrier film characterized by laminating at least one composite polymer layer.   The gas barrier film according to any one of claims 1 to 6, wherein the silicon oxide film has a thickness of 5 to 300 nm.   The gas barrier film according to any one of claims 1 to 7, wherein the composition further contains one or more metal alkoxides.   A gas containing an organic silicon compound having no carbon-silicon bond in the molecule and a gas containing an oxygen atom are used as a raw material gas, and the flow ratio of the gas of the organic silicon compound and the gas containing an oxygen atom is set to 1 to 3 to 1 pair. A process of forming a silicon oxide film by a plasma CVD method on a substrate film introduced into the reaction chamber and arranged in the reaction chamber as a range of 50, and alkoxysilane and silane coupling on the silicon oxide film after film formation Composite polymer of the above composition comprising a linear polymer as a main component, obtained by polycondensation of a composition comprising an agent and polyvinyl alcohol in the presence of a sol-gel catalyst, mineral acid, water, and an organic solvent And then applying a heat treatment to the coating film of the coating liquid at a temperature not lower than 120 ° C. and not higher than the melting point of the base film, and then applying the composition onto the silicon oxide film. The method of manufacturing a gas barrier film, which comprises forming a composite polymer layer.   The method for producing a gas barrier film according to claim 9, wherein the composition further contains one or more metal alkoxides.   The sol-gel catalyst is a tertiary amine that is substantially insoluble in water and soluble in an organic solvent, and forms a coating film of a ting composition. The manufacturing method of the gas barrier film of 9 or 10.   The method for producing a gas barrier film according to claim 9, wherein the water is used in a ratio of 0.8 to 2 moles per mole of alkoxysilane.   The method for producing a gas barrier film according to claim 10, wherein the water is used in a ratio of 0.8 to 2 moles with respect to 1 mole of the total mole amount of alkoxysilane and metal alkoxide. The method for producing a gas barrier film according to any one of claims 9 to 13, wherein the composite polymer layer is further subjected to acetal treatment.

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