JP2005119160A - 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 the 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 1,055-1,065 cm<SP>-1</SP>. A coating film of a gas barrier composition containing an ethylene/vinyl copolymer (a) and a compound (b) represented by the general formula: R<SP>1</SP>mM(OR<SP>2</SP>)n is laminated on the silicone 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.

Invention of Claim 1 solves the subject of the invention regarding said gas barrier film, The base film and the silicon oxide film formed by the plasma CVD method on one side or both sides of the base film The silicon oxide film has a component ratio of 170 to 200 oxygen atoms and 30 or less carbon atoms with respect to 100 silicon atoms, and Si—O—Si stretch between 1055 to 1065 cm ^−1. It has IR absorption based on vibration, and (a) an ethylene / vinyl copolymer and (b) a general formula (1) on the silicon oxide film.
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate The gist is the film.

  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 that exhibits excellent gas barrier properties, and the gas barrier properties are enhanced by a coating film of the gas barrier coating composition.

  According to the first aspect of the invention, the film thickness of the silicon oxide film is set to, for example, 50 nm, and the coating film of the gas barrier coating composition is set to 2 μm. It is possible to provide a gas barrier film that has a higher barrier property and does not deteriorate the barrier property against gases such as oxygen and water vapor even in a humid environment of 90% RH.

Invention of Claim 3 solves the subject regarding a gas barrier film to the above, 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. And (a) an ethylene / vinyl copolymer and (b) a general formula (1) on the vapor deposition film.
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate The gist is the film.

  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 coating film of the gas barrier coating composition.

  According to the third aspect of the present invention, the film thickness of the silicon oxide film is set to, for example, 50 nm, and the coating film of the gas barrier coating composition is set to 2 μm. It is possible to provide a gas barrier film that has a higher barrier property and does not deteriorate the barrier property against gases such as oxygen and 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, and (a) an ethylene-vinyl copolymer on the silicon oxide film, And (b) general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition containing at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate The gist is the film.

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 the excellent gas barrier property as described above, and the gas barrier property is enhanced by the coating film of the gas barrier coating composition.

  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 coating film of the gas barrier coating composition is set to 2 μm. It is possible to provide a gas barrier film that has a higher barrier property and does not deteriorate the barrier property against gases such as oxygen and water vapor even in a humid environment of 90% RH.

Invention of Claim 6 solves the subject regarding 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 a CO molecule of 2341 ± 4 cm ^−1. A silicon oxide film having an IR absorption peak based on the stretching vibration of (a) an ethylene-vinyl copolymer, and (b) a general formula (1) on the silicon oxide film.
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate The gist is the film.

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 described in claim 6 is provided with a silicon oxide film exhibiting excellent gas barrier properties, and the gas barrier properties are further enhanced by the coating film of the gas barrier coating composition.

  According to the sixth aspect of the present invention, the film thickness of the silicon oxide film is set to, for example, 50 nm and the coating film of the gas barrier coating composition is set to 2 μm. It is possible to provide a gas barrier film that has a higher barrier property and does not deteriorate the barrier property against gases such as oxygen and 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 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 coating film of a gas barrier coating composition on the thin silicon oxide film. It is made. 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.

The invention according to claim 8 solves the above-described problem relating to the method for producing a gas barrier film, wherein 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. 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. A process of forming a silicon film, and (a) an ethylene-vinyl copolymer and (b) a general formula (1) on the silicon oxide film after film formation
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier film comprising: a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a gas barrier coating composition containing at least one selected from the group of metal acylates. The manufacturing method is the gist.

  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 the production method of the present invention, it is desirable to subject the deposited silicon oxide film to a heat treatment in a temperature range of 50 ° C. to 200 ° C. before applying the gas barrier coating composition. By this heat treatment, a silicon oxide film having an IR absorption peak based on the stretching vibration of CO molecules and an improvement in oxygen permeability and water vapor permeability can be obtained. In addition, after the gas barrier coating composition is applied, heat treatment may be performed for drying the coating film of the gas barrier coating composition and heat treatment of the silicon oxide film.

  In the production method of the present invention, since the coating film of the gas barrier coating composition is formed on the silicon oxide film, the component (b) in the silicon oxide film and the gas barrier coating composition is subjected to a chemical reaction by hydrolysis / cocondensation reaction. A bond, a hydrogen bond, a coordination bond, or the like is formed, and adhesion between the silicon oxide film and the coating film of the gas barrier coating composition is improved.

  In the production method of the present invention, it is desirable to form a coating film of the gas barrier coating composition using a gas barrier coating composition further containing a nitrogen-containing organic solvent as the gas barrier coating composition. By mixing the nitrogen-containing organic solvent, a good coating film having a transparent appearance can be obtained in coating with a thin film.

  In the production method of the present invention, it is desirable to form a coating film of the gas barrier coating composition using a gas barrier coating composition further containing inorganic fine particles as the gas barrier coating composition.

  In the production method of the present invention, the gas barrier coating composition is prepared by hydrolyzing the component (b) in water or a mixed solution containing water and a hydrophilic organic solvent, and then mixing with the component (a). It is desirable to apply this gas barrier coating composition on the silicon oxide film. When the gas barrier coating composition is prepared as described above, a gas barrier coating composition having no change in viscosity over time and excellent handleability can be obtained.

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 It was formed by a plasma CVD method, a silicon oxide film and the gas barrier Coated with a IR absorption peak based on the stretching vibration of CO molecules in 2341 ± 4 cm ^-1 The coating film of the coating composition is formed into a thin film, and although it is a gas barrier film with a thin film thickness, it has a high barrier property and does not deteriorate the barrier property against gases such as oxygen and water vapor even under humid conditions. A gas barrier film 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 (A) an ethylene-vinyl copolymer, and (b) a general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. The method comprises the steps of applying a gas barrier coating composition containing at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate. Even though it is a thin gas barrier film, it has a high barrier property and does not deteriorate the barrier property against gases such as oxygen and water vapor even under humid conditions. Film can be manufactured. Moreover, cracks can be prevented from entering by making the silicon oxide film thinner. Furthermore, such a thin silicon oxide film is preferable in terms of productivity because it does not impair transparency and appearance, and can suppress an increase in curling of the film. In the production method of the present invention, since the coating film of the gas barrier coating composition is formed on the silicon oxide film, the component (b) in the silicon oxide film and the gas barrier coating composition is subjected to a chemical reaction by hydrolysis / cocondensation reaction. A bond, a hydrogen bond, a coordination bond, or the like is formed, the adhesion between the silicon oxide film and the coating film of the gas barrier coating composition is improved, and a high barrier film having a high gas barrier property can be produced.

  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. Further, on the silicon oxide film 2, (a) an ethylene / vinyl copolymer, and (b) a general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A coating film 3 of a gas barrier coating composition containing at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate is 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 coating film of a gas barrier coating composition 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 has an extremely high gas barrier by laminating a coating film of a gas barrier coating composition on the thin silicon oxide film. Sex is played. 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 coating film 3 of the gas barrier coating composition 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. Furthermore, 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. The component ratio may be any device that can quantitatively measure each component of Si, O, and C, and typical measurement devices include ESCA (Electron Spectroscopy for Chemical For Chemical Analysis) and RBS (Rutherford Back Scattering). , Evaluated by the results measured by Auger 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, the transparency of the entire gas barrier film is required when used in two 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 effect of the silicon film is great.

(C) Gas barrier coating composition coating film The gas barrier coating composition coating film comprises (a) an ethylene-vinyl copolymer (hereinafter referred to as component (a)), and (b) a general formula (1).
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. The gas barrier coating composition contains at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate (hereinafter referred to as component (b)). Here, as the component (a) ethylene / vinyl copolymer which is a component of the gas barrier coating composition, at least one selected from the group of polyvinyl alcohol and ethylene / vinyl alcohol copolymer may be mentioned. The gas barrier coating composition preferably further contains a nitrogen-containing organic solvent. Further, the gas barrier coating composition preferably contains inorganic fine particles (hereinafter referred to as component (c)). The purpose of curing the gas barrier coating composition faster, the purpose of forming a cocondensate of component (a) and component (b), and the ease of forming a cocondensate of component (a) and component (b) For the purpose, a curing agent (hereinafter referred to as component (d)) may be used as an optional component. The combined use of component (d) is effective for curing at a relatively low temperature and obtaining a denser coating film. The gas barrier coating composition will be described below.

[Gas barrier coating composition]
(A) component;
The ethylene / vinyl copolymer as component (a) is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer, and having an acetate group. From partially saponified products remaining several tens of percent to complete saponified products in which only a few mole percent of acetic acid groups remain or no acetic acid groups remain, although not particularly limited, From the viewpoint, the saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter referred to as “ethylene”). The “content” is usually 0 to 50 mol%, preferably 20 to 45 mol%. Specific examples of the ethylene-vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol) %) And the like.

  Component (a) described above: The melt flow index of the ethylene / vinyl copolymer is 1 to 20 g / 10 min, preferably 1 to 18 g / 10 min under the conditions of 210 ° C. and a load of 21.168 N. These component (a) ethylene / vinyl copolymers can be used alone or in combination of two or more.

  The ethylene / vinyl copolymer constituting the component (a) itself is excellent in gas barrier properties, weather resistance, organic solvent resistance, transparency, gas barrier properties after heat treatment, and the like. In addition, when (a) the ethylene-vinyl copolymer is used to cure the coating film of the gas barrier coating composition, the hydroxyl group present in the repeating unit derived from the polyvinyl alcohol has a component (b) and / or ( Co-condensation with the component c) can provide excellent coating performance.

  The proportion of the component (a) in the gas barrier coating composition is 10 to 10,000 parts by weight, preferably 20 to 5,000 parts by weight, more preferably 100 to 1, parts by weight based on 100 parts by weight of the component (b) described later. 000 parts by weight. If it is less than 10 parts by weight, cracks are likely to occur in the resulting coating film, and the gas barrier property is lowered. .

(B) component;
The component (b) is a metal alcoholate represented by the above general formula (1), a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, and a hydrolysis of the chelate compound Or at least one selected from the group of metal acylates. That is, the component (b) may be only one of these six types, or may be a mixture of any two or more types. Here, the hydrolyzate of the metal alcoholate does not need to have all the OR ² groups contained in the metal alcoholate hydrolyzed. For example, only one is hydrolyzed, and two or more are hydrolyzed. It may be decomposed or a mixture thereof. In addition, the metal alcoholate condensate is a product in which the M-OH group of the metal alcoholate hydrolyzate is condensed to form an M-O-M bond, but all of the M-OH groups are condensed. However, it is a concept including a mixture of a small part of M-OH groups, a mixture of those having different degrees of condensation, and the like. Furthermore, the metal alcoholate chelate compound is at least one selected from metal alcoholates and β-diketones, β-ketoesters, hydroxycarboxylic acids, hydroxycarboxylic acid salts, hydroxycarboxylic acid esters, ketoalcohols and aminoalcohols. Obtained by reaction with seed compounds. Among these compounds, β-diketones or β-ketoesters are preferably used, and specific examples thereof include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, and acetoacetate-i-propyl. , Acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4- Examples include octane-dione, 2,4-nonane-dione, and 5-methyl-hexane-dione. Further, the hydrolyzate of the chelate compound does not have to be hydrolyzed in all of the OR ² groups contained in the chelate compound, like the hydrolyzate of the metal alcoholate. For example, only one may be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. The component (b) is considered to act to form a cocondensate with the component (a).

In the general formula (1), examples of the metal atom represented by M include zirconium, titanium, and aluminum, and titanium is particularly preferable. The monovalent organic group having 1 to 8 carbon atoms of R ¹ is different depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. When the metal compound is a metal alcoholate, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group; vinyl group, allyl group In addition to groups, cyclohexyl groups, phenyl groups, glycidyl groups, (meth) acryloxy groups, ureido groups, amide groups, fluoroacetamide groups, isocyanates, etc., substituted derivatives of these groups, and the like can be mentioned. Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, A ureido group, an ammonium base, etc. can be mentioned. However, carbon number of R < ¹ > which consists of these substituent derivatives is 8 or less including the carbon element in a substituent. Next, when the metal compound is a metal acylate, the monovalent organic group having 1 to 8 carbon atoms of R ¹ includes an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, and a benzoyloxyl group. And acyloxyl groups such as a trioyloxyl group. In the general formula (1), when two R ^{1 s} are present, they may be the same as or different from each other.

The alkyl group having 1 to 5 terminal primes of R ² includes, for example, a methyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl group. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. A plurality of R ² present in the general formula (1) may be the same as or different from each other.

Among the above-mentioned component (b), as specific examples of metal alcoholates and metal alcoholate chelate compounds,
(I) Tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n -Zirconium compounds such as propylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
(B) Tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetonate) Titanium compounds such as titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy bislactate titanium, dihydroxy titanium lactate, tetrakis (2-ethylhexyloxy) titanium;
(C) Tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum, di-i-propoxy acetylacetonate aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis ( Examples thereof include aluminum compounds such as ethylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetoacetonato) aluminum, monoacetylacetonato-bis (ethylacetoacetate) aluminum.

  Among these metal alcoholates and metal alcoholate chelate compounds, preferred are tri-n-butoxy ethylacetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy Mention may be made of bis (triethanolaminato) titanium, dihydroxybislactatetitanium, di-i-propoxyethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum. Particularly preferred compounds are titanium compounds such as di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxy bislactatetotitanium.

  Specific examples of metal acylates include dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, and di-i. -Propoxy titanium dimalonate, di-i-propoxy titanium dibenzoylate, di-n-butoxy zirconium diacetate, di-i-propylaluminum monomalonate and the like. Particularly preferred compounds are titanium compounds such as dihydroxy-titanium dibutyrate and di-i-propoxy-titanium diacetate. These components (b) are used singly or in combination of two or more.

As the component (b), it is preferable to use a coating solution hydrolyzed in water or a mixed solvent containing water and a hydrophilic solvent, which will be described later, because the coating liquid has little change with time in viscosity and is easy to handle. In this case, the amount of water, compared R ¹ mM (OR ²⁾ n1 moles, 0.1 to 1,000 mol, preferably 0.5 to 500 moles. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is water / hydrophilic organic solvent = 10 to 90/90 to 10 (weight ratio), preferably 30 to 70/70 to 30, more preferably. 40-60 / 60-40.

(C) component;
The gas barrier coating composition preferably contains inorganic fine particles as component (c). The inorganic fine particles are fine particle inorganic substances having an average particle diameter of 0.2 μm or less and substantially free of carbon atoms, and examples thereof include metals or silicon oxides, metals or silicon nitrides, and metal borides. For example, in order to obtain silicon oxide, a method for producing inorganic fine particles includes a gas phase method obtained by hydrolyzing silicon tetrachloride in a flame of oxygen and hydrogen, a liquid phase method obtained by ion exchange of sodium silicate, and a silica gel mill. Examples of the production method include a solid phase method obtained by pulverization using a method such as, but are not limited to these methods.

Specific examples of compounds of component _{(c), SiO 2, Al 2 O 3} , TiO 2, WO 3, Fe 2 O 3, ZnO, NiO, RuO 2, CdO, SnO 2, Bi 2 O 3, 3Al ₂ O ₃ .2SiO ₂ , Sn—In ₂ O ₃ , Sb—In ₂ O ₃ , oxide such as CoFeO _x , nitride such as Si ₃ N ₄ , Fe ₄ N, AlN, TiN, ZrN, TaN, Ti Examples thereof include borides such as ₂ B, ZrB ₂ , TaB ₂ , and W ₂ B. Examples of the form of the inorganic fine particles include powder, water, colloid or sol dispersed in an organic solvent, but are not limited thereto. Among these, in order to obtain an excellent film forming ability by co-condensing with the component (a) and / or the component (b), preferably colloidal alumina, alumina sol, tin sol, zirconium sol, pentoxide Colloidal oxides having a hydroxyl group on the particle surface, such as antimony sol, cerium oxide sol, zinc oxide sol, and titanium oxide sol are used. The average particle diameter of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm or less. If the average particle diameter exceeds 0.2 μm, the gas barrier property may be inferior.

(D) component;
(D) Component curing accelerators include inorganic acids such as hydrochloric acid; alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide ; Acidic compounds such as alkyl titanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, metaphenylenediamine, ethanolamine , Triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyl Zimetoki Silane, amine compounds such as γ- anilino _{trimethoxysilane, (C 4 H 9) 2} Sn (OCOC 11 H 23) 2, (C 4 H 9) 2 Sn (OCOCH = CHCOOCH 3) 2, (C _{4 H 9) 2 Sn (OCOCH} = CHCOOCC 4 H 9) 2, (C 8 H 17) 2 Sn (OCOC 11 H 23) 2, (C 8 H 17) 2 Sn (OCOCH = CHCHCOOCH 3) 2, (C _{8 H 17) 2 Sn (OCOCH} = CHCOOC 4 H 9) 2, (C 8 H 17) 2 Sn (OCOCH = CHCOOC 8 H 17) 2, Sn (OCOCC 8 H 17) carboxylic acid type organic tin compounds such as ₂ (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (S _{CH 2 COOC 12 H 25) 2} ,
(C ₄ H ₉ ) Sn (SCH ₂ COOC ₈ H ₁₇ )
｜
O
｜
(C ₄ H ₉ ) Sn (SCH ₂ COOC ₈ H ₁₇ )
Mercapto-type organotin compounds such as
_{(C 4 H 9) (C} 8 H 17) (C 4 H 9) -Sn = S
\ \ |
Sn = S, Sn = S, S
/ / |
_{(C 4 H 9) (C} 8 H 17) (C 4 H 9) -Sn = S
Sulfide type organotin compounds such as
Organic tin such as a reaction product of an organic tin oxide such as (C ₄ H ₉ ) ₂ SnO or (C ₈ H ₁₇ ) ₂ SnO and an ester compound such as ethyl silicate, dimethyl maleate, diethyl maleate, or dioctyl phthalate Compounds etc. are used. The ratio of the component (d) in the gas barrier coating composition is usually 0.5 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the solid content of the gas barrier coating composition. It is.

  Furthermore, the above-mentioned β-diketones and / or β-ketoesters can be added to the gas barrier coating composition as a stability improver. That is, by coordinating to the metal atom in the metal alcoholate present in the composition as the component (b), it acts to control the condensation reaction between the component (a) and the component (b). It is considered that it acts to improve the storage stability of the resulting composition. The amount of the β-diketone and / or β-ketoester mentioned above is preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal atom in the component (b).

  The gas barrier coating composition is usually obtained by dissolving and dispersing the above components (a) to (b) and optionally the component (c) in water and / or a hydrophilic organic solvent solvent. Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, diacetone alcohol, ethylene glycol, diethylene glycol, triglyceride. C1-C8 saturated aliphatic monohydric or dihydric alcohols such as ethylene glycol; C1-C8 saturated aliphatic ether compounds such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether; ethylene glycol Ester compounds of saturated aliphatic dihydric alcohols having 1 to 8 carbon atoms such as monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; N, N-dimethyl Nitrogen-containing compounds (nitrogen-containing organic solvents) such as acetoamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, pyridine; sulfur-containing compounds such as dimethyl sulfoxide; lactic acid, methyl lactate, ethyl lactate, salicylic acid, Examples thereof include hydroxycarboxylic acid esters such as methyl salicylate. Among these, preferred are saturated aliphatic monohydric alcohols having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and the like. And nitrogen-containing compounds (nitrogen-containing organic solvents) such as N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, N-methylpyrrolidone, and pyridine.

  These water and / or hydrophilic organic solvent are more preferably used by mixing water and a hydrophilic organic solvent. The preferred solvent composition is water / monohydric alcohol having 1 to 8 carbon atoms and water / nitrogen-containing compound (nitrogen-containing nitrogen organic solvent). More preferably, it is water / a saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms / nitrogen-containing compound (nitrogen-containing organic solvent). By mixing the nitrogen-containing organic solvent, a good coating film having a transparent appearance can be obtained in coating with a thin film.

  The amount of water and / or hydrophilic organic solvent used is such that the total solid content of the composition is preferably 60% by weight or less. For example, when it is used for the purpose of forming a thin film of a coating film of the gas barrier coating composition, it is usually 5 to 40% by weight, preferably 10 to 30% by weight, and the thick film of the coating film of the gas barrier coating composition When used for the purpose of formation, it is usually 20 to 50% by weight, preferably 30 to 45% by weight. When the total solid content concentration of the composition exceeds 60% by weight, the total solid content stability of the composition tends to decrease. The ratio of the nitrogen-containing organic solvent is usually 1 to 70% by weight, preferably 5 to 50% by weight, based on the total amount of the solvent.

  The organic solvent is preferably water and / or a hydrophilic solvent as described above. In addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as tetrahydrofuran and dioxane, acetone, and the like. Also, ketones such as methyl ethyl ketone, esters such as ethyl acetate and butyl acetate can be used.

  As described above, the gas barrier coating composition comprises the above components (a) to (b) and, optionally, the components (a) to (b) added with the component (c), water and / or It is obtained by mixing in a hydrophilic organic solvent. Preferably, the components (a) to (b) are added, and the component (c) is added to the components (a) to (b) as necessary. It is obtained by hydrolysis and / or condensation in a hydrophilic organic solvent. The reaction conditions at this time are a temperature of 20 to 100 ° C., preferably 30 to 80 ° C., and a time of 0.1 to 100 ° C., preferably 1 to 10 hours. The weight average molecular weight of the obtained gas barrier coating composition is a polymethyl methacrylate conversion value by a general GPC method (gel permeation chromatography), and is usually 500 to 1,000,000, preferably 1,000 to 300,000.

  The gas barrier coating composition is filled with components other than the above component (c) in order to develop various properties such as coloring of the obtained coating film, thickening of the coating film, prevention of UV transmission to the base, provision of anticorrosion, and heat resistance. It is also possible to add and disperse the material. Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments or pigments, particulate, fibrous or scale-like metals and alloys, and oxides, hydroxides, carbides, nitrides thereof, and the like. Examples thereof include sulfides. Specific examples of these fillers include particulate, fibrous or scale-like, iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, oxidation Chromium, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, Magnesium carbonate, barium sulfate, bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, chellet green, green earth, manganese green, pigment green, ultramarine, bituminous, pigment green, rock ultramarine, Cobalt blue, cerulean blue, copper borate, molybdenum blue, sulfur Copper, Cobalt Purple, Mars Purple, Manganese Green, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide , Cadmium red, selenium red, chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese Examples thereof include white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

  The average particle diameter or average length of these fillers is usually 50 to 50,000 nm, preferably 100 to 50,000 nm, preferably 100 to 5,000 nm. The ratio of the filler in the gas barrier composition is preferably 0.1 to 300 parts by weight, more preferably 1 to 200 parts by weight, with respect to 100 parts by weight of the total solid content of components other than the filler.

  Furthermore, the gas barrier coating composition includes other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, other than the above, silane coupling agents, titanium coupling agents, dyes, dispersions Additives such as an agent, a thickener, and a leveling agent can also be blended.

  In preparing the gas barrier coating composition, a composition containing the above components (a) to (b), preferably (a) to (c) may be prepared. Preferably, the component (b) is added. After hydrolysis in water or a mixed solvent containing water and a hydrophilic organic solvent, the component (a) is mixed. By doing so, there is no change in viscosity of the gas barrier coating composition over time, and a gas barrier coating composition excellent in handleability can be obtained. Specific examples of the method for preparing the gas barrier coating composition in the case of using the component (c) include the following [1] to [4]. The component (b) used in these preparation methods may be hydrolyzed in advance in water or a mixed solvent containing water and a hydrophilic organic solvent.

(Method for preparing gas barrier coating composition)
[1] A method of adding the component (b) after adding the component (c) to the component (a) dissolved in water and / or a hydrophilic organic solvent.
[2] A method in which the component (c) is added to the component (a) dissolved in water and / or a hydrophilic organic solvent, and then the component (b) is added, followed by hydrolysis and / or condensation.
[3] A method in which the component (c) is added to the component (b) dissolved in water and / or a hydrophilic organic solvent, followed by hydrolysis and / or condensation, and then the component (a).
[4] A method in which the components (a) to (c) are added all at once to water and / or a hydrophilic organic solvent and dissolved and dispersed. Or the method of performing hydrolysis and / or condensation after that.

  In order to form a coating film of the gas barrier coating composition on the silicon oxide film using the gas barrier coating composition described above, roll coating such as gravure coater, spray coating, spin coating, dipping is performed on the surface of the silicon oxide film. A coating film of a gas barrier composition having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm is formed by one or a plurality of times of coating by a coating means such as a brush, a bar coat, or an applicator. be able to. If necessary, a printed pattern layer may be provided on the coating film of the gas barrier coating composition, and if necessary, a heat sealable resin layer may be formed on the printed pattern layer.

  The above-mentioned printed pattern layer uses, for example, a normal gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, and other ink compositions on the coating film of the gas barrier coating composition. For example, a gravure printing method, an offset printing method, a relief printing method, a silk screen printing method, and other printing methods may be used to form, for example, characters, figures, patterns, symbols, and other desired printing patterns. it can. Examples of the vehicle for the ink composition include polyolefin resins such as polyethylene resins and chlorinated polypropylene resins, poly (meth) acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, and vinyl chloride-vinyl acetate. Polymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin , Epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin, urea resin, polyurethane resin, phenolic resin, xylene resin, maleic acid resin, nitrocellulose, ethylcellulose A Fibrous resins such as butylbutyl cellulose and ethyloxyethyl cellulose, rubber resins such as chlorinated rubber and cyclized rubber, natural resins such as petroleum resins, rosin and casein, oils and fats such as linseed oil and soybean oil, and other A mixture of one or more resins can be used. Add one or more colorants such as dyes and pigments to one or more of the above-mentioned vehicles, and if necessary, fillers, stabilizers, plasticizers, antioxidants, UV absorbers, etc. Light stabilizers, dispersants, thickeners, drying agents, lubricants, antistatic agents, crosslinking agents, and other additives, and various forms of ink compositions kneaded with solvents, diluents, etc. Can be used for the formation of the printed picture layer.

  Next, as the heat-sealable resin for forming the heat-sealable resin layer, any resin can be used as long as it melts by heat and exhibits fusion properties. (Linear) Low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer Polymers, methylpentene polymers, acid-modified polyolefin resins obtained by modifying polyolefin resins such as polyethylene and polypropylene with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and other unsaturated carboxylic acids, Polyvinyl acetate resin, polyester resin, polyester Styrene resin can be used singly or two other resins. As the heat sealable resin, one or more of the above-described resins are used. For example, the resin formed into a film on the coating film of the gas barrier coating composition by an inflation method, a T-die method, or other methods. It can be used in the form of a film, a sheet, or a coating film made of a resin composition containing one or more of the above-described resins. The film thickness is about 5 to 100 μm, preferably about 10 to 50 μm.

  Among the above resins, it is particularly desirable to use linear (linear) low density polyethylene. Linear low density polyethylene has the advantage that it has less adhesive propagation and improved impact resistance, and when a gas barrier film is used as a packaging material, it is a heat seal resin that forms the inner layer. Since the layer is always in contact with the contents, it is also effective for preventing deterioration of the environmental stress cracking resistance. Also, other resins can be blended with the linear low density polyethylene. For example, blending with an ethylene-butene copolymer or the like slightly deteriorates the heat stability and seal stability under high temperature environment. Although there is a tendency, there exists an advantage that tearability improves and it contributes to easy openability. Specifically, as the linear low density polyethylene as the heat-sealable resin as described above, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst can be used. Specifically, the product name “Kernel” manufactured by Mitsubishi Chemical Corporation, the product name “Evolue” manufactured by Mitsui Petrochemical Co., Ltd., and the product name “EXACT” manufactured by EXON CHEMICAL, USA. ”, An ethylene-α / olefin copolymer polymerized using a metallocene catalyst such as“ AFFINITY ”or“ engage ”manufactured by Dow Chemical Co., USA can do. When the ethylene-α / olefin copolymer polymerized using the metallocene catalyst is used, there is an advantage that low-temperature heat sealability is possible when a bag is produced.

(Laminated material)
The gas barrier film according to the first aspect of the present invention can be laminated with other materials to form a desired laminated material. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene -Acrylic acid copolymer, ethylene-methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, Poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer copolymer (ABS resin), polyester resin, Polyamide resin Any of known resin films or sheets such as polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. You can choose to use. In addition, for example, cellophane, polycello, synthetic paper, and the like can be used. The film or sheet can be any of an unstretched film or sheet, a uniaxially stretched film or sheet, or a biaxially stretched film or sheet. The thickness is arbitrary, but can be selected from a range of several μm to 300 μm. As the film or sheet, any of extrusion film formation, inflation film formation, or coating film can be used.

  In addition, when the gas barrier film of the present invention is used for applications such as packaging materials that require flexibility, the thickness is set to 5 to 30 nm in consideration of the mechanical properties and applications of the formed silicon oxide film. It is more preferable. By setting the thickness of the silicon oxide film to 5 to 30 nm, flexibility as a flexible packaging material can be provided, and generation of cracks when the film is bent can be prevented. In addition, the gas barrier film of the present invention is not required to be relatively thin, but uses where gas barrier properties are required preferentially, such as a gas barrier film for film liquid crystal displays, a gas barrier film for film organic EL displays, or a gas barrier for film solar cells. Even when used for applications such as a film, a gas barrier film having a silicon oxide film that is thicker than the aforementioned 5 to 30 nm, for example, about 50 nm can be applied.

  By using the gas barrier film of the present invention for the above applications, it is possible to make the gas barrier property of the same level thinner than that of the conventional product.

As a method for producing a laminated material using the gas barrier film of the present invention, for example, a dry lamination method in which lamination is performed through an adhesive layer for lamination, an extrusion lamination method in which lamination is performed through a melt-extruded resin layer, or the like is applied. be able to. In the dry lamination method, as a laminating adhesive, for example, one-pack type or two-pack type cured or non-cured vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, Epoxy-based, rubber-based and other solvent-type, aqueous-type, and emulsion-type adhesives for laminating can be used. Coating of the adhesive for laminating can be performed by, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, or other methods. The coating amount of the laminating adhesive is preferably about 0.1 to 10 g / m ² (dry state), more preferably about 1 to 5 g / m ² (dry state). In addition, for example, an adhesion promoter such as a silane coupling agent can be arbitrarily added to the laminating adhesive. In the extrusion lamination method, a heat-sealable resin can be used as the melt-extruded adhesive resin, and it is preferable to use low-density polyethylene, particularly linear low-density polyethylene, or acid-modified polyethylene. The film thickness of the melt-extruded resin layer is preferably about 5 to 100 μm, more preferably about 10 to 50 μm. When it is necessary to obtain stronger adhesive strength at the time of the above lamination, an adhesion improver such as an anchor coating agent can be coated. Examples of the anchor coating agent include organic titanium anchor coating agents such as alkyl titanates, isocyanate anchor coating agents, polyethyleneimine anchor coating agents, polybutadiene anchor coating agents, and other various water-based or oil-based anchor coating agents. Can be used. The anchor coating agent layer can be formed by coating the above-mentioned anchor coating agent on a silicon oxide film by roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating methods, and drying. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

  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. It has advantages. 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 bag making and box making method using the gas barrier film of the present invention or the laminate material using the gas barrier film will be described. For example, in the case of soft packaging, the gas barrier film of the present invention having a heat-sealable resin layer or the Use a laminated material using a gas barrier film, fold the gas barrier film or laminated material with the inner heat-sealable resin layer facing each other, or overlap the two gas barrier films or laminated materials Furthermore, the peripheral edge part can be heat-sealed to constitute a bag body. In that case, the peripheral edge of the outer periphery of the bag body is a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), a pleated seal type, Various packaging containers can be manufactured by heat sealing using a flat bottom sealing type, a square sealing type, and other heat sealing modes. Moreover, the said laminated material is applicable also to manufacture of a self-supporting packaging bag, a tube container, etc. As a heat sealing method, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used. Furthermore, the packaging container can be formed in any form, for example, a one-piece type or a two-piece type, and a spout, an opening / closing zipper, and the like can be arbitrarily attached.

  When manufacturing a packaging container including a paper base material, a laminated material including a paper base material is used, and a blank board of a desired paper container is manufactured from the laminated material. Various types of liquid paper containers such as a brick type, a flat type, and a gable top type can be manufactured by boxing the head, bottom, and head. The packaging container produced as described above can be used for various foods and drinks, chemicals such as adhesives and pressure-sensitive adhesives, pharmaceuticals, miscellaneous goods, and other various filled packaging.

  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 coating film 3 of a gas barrier coating composition, as in the gas barrier film of the invention described in claim 1, provided that the vapor deposition film 4 is shown in FIG. And as shown in FIG. 3, a vapor deposition film is a vapor deposition film formed in the single side | surface or both surfaces of the base film by plasma CVD method, Comprising: The grain 4a (with a space | interval of 5-40 nm on the surface of the vapor deposition film 4 is used. grain) is formed.

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 coating film 3 of the gas barrier coating composition are the same as those described for the base film 1 and the coating film 3 of the gas barrier coating composition according to claim 1, the 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. Further, a bag made of a gas barrier film of the invention according to claim 3 or a laminate made using the gas barrier film, a bag making method, a heat-sealing form of a packaging bag, and a packaging made of a laminate containing a paper substrate. Since the production of the container and the like are the same as in the case of the gas barrier film according to the invention described in claim 1, the 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. 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 comprises a base film 1, a silicon oxide film 5, and a coating film 3 of a gas barrier coating composition, as in the gas barrier film of the invention described in claim 1, provided that the silicon oxide film 5 is It has an E ′ center observed by electron spin resonance (ESR) 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 coating film 3 of the gas barrier coating composition are the same as those described for the base film 1 and the coating film 3 of the gas barrier coating composition according to claim 1, the 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. 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. Moreover, the packaging which consists of a laminated material containing the bag making, the box making method, the heat seal form of a packaging bag, and a paper base material using the gas barrier film of the invention of claim 5 or the laminated material using the gas barrier film. Since the production of the container and the like are the same as in the case of the gas barrier film according to the invention described in claim 1, the 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. 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 consists of a base film 1, a silicon oxide film 6, and a coating film 3 of a gas barrier coating composition, similar to the gas barrier film of the invention described in claim 1, provided that the silicon oxide film 6 is It is characterized in that there is a peak of IR absorption based on stretching vibration of CO molecules at 2341 ± 4 cm ⁻¹ .

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 coating film 3 of the gas barrier coating composition are the same as those described for the base film 1 and the coating film 3 of the gas barrier coating composition according to claim 1, the 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. 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. Moreover, the packaging which consists of a laminated material containing the bag making, the box making method, the heat-sealing form of a packaging bag, the paper base material using the gas barrier film of the invention of Claim 6, or the laminated material using this gas barrier film Since the production of the container and the like are the same as in the case of the gas barrier film according to the invention described in claim 1, the 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. 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 8)
The gas barrier film of the present invention has any one of the above-described four embodiments of the vapor deposition film or a vapor deposition film having a plurality of features of these embodiments simultaneously, and (a) an ethylene-vinyl copolymer on the vapor deposition film. And (b) general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A coating film of a gas barrier coating composition containing at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate is formed. As a method for forming this vapor deposition film, various methods as described above can be used. However, it is particularly preferable for any of the embodiments to be formed by plasma CVD. Hereinafter, (a) the deposition process of the deposited film and (b) the formation process of the coating film of the gas barrier coating composition 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 ones such as tetramethyldisiloxane and normal methyltrimethoxysilane 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 peak disappears varies greatly depending on the heat treatment temperature, but if it is 5 minutes or longer, 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 the formation after the coating film of the gas barrier coating composition mentioned later.

(Formation process of coating film of barrier coating composition)
A coating film of the barrier coating composition is formed on the deposited film.
The coating film of the gas barrier coating composition comprises (a) an ethylene / vinyl copolymer, and (b) a general formula (1).
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, and a metal alcoholate represented by a group or a phenyl group, wherein m and n are each an integer of 0 or more, and m + n is a valence of M) The gas barrier coating composition comprises at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate. This gas barrier coating composition preferably further contains a nitrogen-containing organic solvent. Further, the gas barrier coating composition preferably contains inorganic fine particles. The purpose of curing the gas barrier coating composition faster, the purpose of forming a cocondensate of component (a) and component (b), and the ease of forming a cocondensate of component (a) and component (b) For the purpose, a curing agent (component (d)) may be used as an optional component. The combined use of the component (d) is effective for curing at a relatively low temperature and obtaining a denser coating film. The details of the gas barrier coating composition are as described in detail in paragraphs [0050] to [0072]. The preparation of the gas barrier coating composition is as described in paragraphs [0073] and [0074]. The gas barrier coating composition will be described below.

  As described in paragraph [0075], a printed pattern layer may be provided on the coating of the gas barrier coating composition. Further, as described in paragraphs [0075] to [0078], a heat seal layer can be provided on the coating film of the gas barrier coating composition.

  Further, as described in paragraphs [0079] to [0083], other materials can be laminated on the cover film of the present invention to form a laminated material.

  In the production method of the present invention, since the coating film of the gas barrier coating composition is formed on the silicon oxide film, the component (b) in the silicon oxide film and the gas barrier coating composition is subjected to a chemical reaction by hydrolysis / cocondensation reaction. A bond, a hydrogen bond, a coordination bond, or the like is formed, and adhesion between the silicon oxide film and the coating film of the gas barrier coating composition is improved.

  In the production method of the present invention, it is desirable that a gas barrier coating composition further containing a nitrogen-containing organic solvent is used as the gas barrier coating composition to form a coating film of the gas barrier coating composition. By mixing the nitrogen-containing organic solvent, a good coating film having a transparent appearance can be obtained in coating with a thin film.

  In the production method of the present invention, it is desirable to form a coating film of the gas barrier coating composition using a gas barrier coating composition further containing inorganic fine particles as the gas barrier coating composition.

  In the production method of the present invention, the gas barrier coating composition is prepared by hydrolyzing the component (b) in water or a mixed solution containing water and a hydrophilic organic solvent, and then mixing with the component (a). It is desirable to apply a coating composition on the silicon oxide film. When the gas barrier coating composition is prepared as described above, a gas barrier coating composition having no change in viscosity over time and excellent handleability can be obtained.

  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 gas barrier coating compositions used in Examples 1 to 4 and Comparative Examples 1 to 4 described later will be described with reference to Reference Examples 1 to 7.

[Reference Example 1: Preparation of titanium chelate compound]
100 parts of tetra-i-propoxytitanium and 70 parts of acetylacetone were added to a reactor equipped with a once-through cooler and a stirrer, and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound (b-1). The purity of this reaction product was 75%.

[Reference Example 2: Preparation of zirconium chelate compound]
To a reactor equipped with a once-through cooler and a stirrer, 100 parts of tetra-n-butoxyzirconium (purity 100%) and 68 parts of ethyl acetoacetate were added and stirred at 60 ° C. for 30 minutes to obtain a zirconium chelate compound (b-2). Obtained. The reaction product was 77%.

[Reference Example 3: Preparation of gas barrier coating composition (A)]
(A) Ethylene / vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Soarnol D2908, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index: 8 g / 10 min. ] 100 parts of 15% water / n-propyl alcohol (weight ratio = 6/4) and 10 parts of the titanium chelate compound (b-1) of Reference Example 1 as the component (b) were mixed on the silicon oxide film. A gas barrier coating composition (A) to be applied was obtained.

[Reference Example 4: Preparation of gas barrier coating composition (B)]
(A) Ethylene / vinyl alcohol copolymer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Soarnol D2908, degree of saponification: 98% or more, ethylene content: 29 mol%, melt flow index: 8 g / 10 min. ] 15% water / n-propyl alcohol solution / N, N-dimethylformamide solution (water / n-propyl alcohol / N, N-dimethylformamide solution, water / n-propyl alcohol / N, N-dimethylformamide weight ratio) = 6/3/1) 100 parts of component (b) and 10 parts of the titanium chelate compound (b-1) of Reference Example 1 were mixed to obtain a gas barrier coating composition (B) to be applied on the silicon oxide film. .

[Reference Example 5: Preparation of (C) of gas barrier coating composition]
In Reference Example 3, a gas barrier coating composition (on the silicon oxide film) applied in the same manner as in Reference Example 3 except that 10 parts of the zirconium chelate compound (b-2) of Reference Example 2 was used as the component (b). C) was obtained.

[Reference Example 6: Preparation of gas barrier coating composition (D)]
A 15% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 6/4) of the ethylene / vinyl alcohol copolymer used in Reference Example 3 was compared with the gas barrier coating composition (D) for comparison. did.

[Reference Example 7: Preparation of gas barrier coating composition (E)]
Except for using 100 parts of a 15% aqueous solution of a polyvinyl alcohol polymer (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Gohsenol NL-05) in which ethylene is not copolymerized in place of component (a) in Reference Example 3. In the same manner as in Reference Example 3, a comparative gas barrier coating composition (E) was obtained.

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 composition (A) prepared in Reference Example 3 was applied onto the silicon oxide film formed by a bar coater, and dried at 100 ° C. for 10 minutes with a hot air drier to form a 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 gas barrier coating composition (A) prepared in Reference Example 3 was applied and dried to obtain the 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 gas barrier coating composition (B) prepared in Reference Example 4 was used instead of the gas barrier coating composition (A).

  A gas barrier film of Example 4 was obtained in the same manner as in Example 1 except that the gas barrier composition (C) prepared in Reference Example 5 was used instead of the gas barrier coating composition (A).

[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 gas barrier coating composition (D) prepared in Reference Example 6 was used instead of the gas barrier coating composition (A).

[Comparative Example 4]
A gas barrier film of Comparative Example 4 was obtained in the same manner as in Example 1 except that the gas barrier coating composition (E) prepared in Reference Example 7 was used instead of the gas barrier coating composition (A) as the gas barrier coating composition.

[Comparative Example 5]
A gas barrier coating film of Comparative Example 5 was obtained in the same manner as in Example 1 except that the gas barrier coating composition (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.

  The IR measurement uses a silicon oxide film before application of the gas barrier coating composition as a sample, and a Fourier transform infrared spectrophotometer (ATR-300 / H, manufactured by JASCO Corporation) equipped with an ATR (multiple reflection) measuring device ( This was performed by JASCO, 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 was obtained by measuring the transmittance and the reflectance with an optical spectrometer (manufactured by Shimadzu Corporation, UV-3100PC) using the silicon oxide film before the gas barrier coating composition was applied as a sample. From the measurement results of the refractive index and 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. A silicon oxide film before application of the gas barrier coating composition was used as a sample, and the surface of the silicon oxide film was first treated with an aqueous ammonium fluoride 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 Instrument)), and the distance between peaks of two adjacent grains having substantially the same peak height was measured. .

  A silicon oxide film before application of the gas barrier coating composition was used as a sample, and 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 (made by HEWLETT PACKERD), ER035M Gauss meter (made by BRUKER, ESR910), and cryostat (made 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 E ′ center spin number by the film thickness and the measurement area is obtained as the 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 gas barrier coating film thickness of 2.0 μm, the oxygen permeability under the condition of 0% RH 0.6 cc / m ² / day / atm, having an oxygen permeability of 0.8 cc / m ² / day / atm under the conditions of 90% RH, and having a water vapor permeability of 0.8 cc / m ² / day / atm, It was found to have 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 silicon oxide film having a thickness of 50 nm and a gas barrier coating film having a thickness of 2.0 μm, the oxygen permeability under the condition of 0% RH is 0.7 cc / m ² / day / atm, having an oxygen permeability of 0.8 cc / m ² / day / atm under the conditions of 90% RH, and having a water vapor permeability of 0.7 cc / m ² / day / atm, It was found to have 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 with a silicon oxide film of 50 nm and a gas barrier coating film thickness of 2.0 μm, the oxygen permeability under the condition of 0% RH is 0.5 c / m ² / day / atm, having an oxygen permeability of 0.7 cc / m ² / day / atm under the conditions of 90% RH, and having a water vapor permeability of 0.8 cc / m ² / day / atm, It was found to have 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 with a silicon oxide film of 50 nm and a gas barrier coating film thickness of 2.0 μm, the oxygen permeability under the condition of 0% RH 0.5 cc / m ² / day / atm, having an oxygen permeability of 0.5 cc / m ² / day / atm under the conditions of 90% RH, and having a water vapor permeability of 0.6 cc / m ² / day / atm, It was found to have 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 40 nm.

The gas barrier film of Comparative Example 1, a silicon oxide film, the oxygen permeability under conditions of ^{RH 0% 1.3cc / m 2 /} day / atm, under conditions of 90% RH oxygen permeability 1.7 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.

As for the gas barrier film of Comparative Example 2, the silicon oxide film has an oxygen permeability of 1.6 cc / m ² / day / atm under the condition of 0% RH and an oxygen permeability of 1.8 cc / m ² under the condition of 90% RH. The water vapor permeability was 1.5 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 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.

In the gas barrier film of Comparative Example 3, the silicon oxide film had a low oxygen permeability of 0.8 cc / m ² / day / atm under the condition of 0% RH, but the oxygen permeability under the condition of 90% RH was 1 It was found to be as high as ³ cc / m ² / day / atm. Further, the water vapor permeability was as high as 1.3 cc / m ² / day / atm, and it was found that the gas barrier was low as compared with 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 .

Regarding the gas barrier film of Comparative Example 4, the silicon oxide film had a low oxygen permeability of 0.7 cc / m ² / day / atm under the condition of 0% RH, but the oxygen permeability under the condition of 90% RH was It was found to be as high as 1.3 cc / m ² / day / atm. Further, the water vapor permeability was as high as 1.6 cc / m ² / day / atm, and it was found that the gas barrier was 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 1063 cm ⁻¹ and the refractive index was 1.47. The E ′ center density was 2.3 × 10 ¹⁶ .

Regarding the gas barrier film of Comparative Example 5, the silicon oxide film had a low oxygen permeability of 0.7 cc / m ² / day / atm under the condition of 0% RH, but the oxygen permeability under the condition of 90% RH was It was found to be as high as 1.8 cc / m ² / day / atm. Further, the water vapor permeability was as high as 1.5 cc / m ² / day / atm, and it was found that the gas barrier was 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 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 Coating film of gas barrier coating composition 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 electrode

Claims (13)

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 (a) an ethylene-vinyl copolymer is formed on the silicon oxide film. Polymer and (b) general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate the film.   The gas barrier film according to claim 1, wherein the silicon oxide film has a refractive index of 1.45 to 1.48. A substrate film; and a deposited film formed on one surface or both surfaces of the substrate film by a plasma CVD method and having grains on the surface with an interval of 5 to 40 nm, and (a) on the deposited film Ethylene-vinyl copolymer and (b) general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate 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 ³ and a more than a silicon oxide film, (a) an ethylene-vinyl copolymer on the silicon oxide film, and (b) the general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate the film. 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. (A) an ethylene-vinyl copolymer and (b) a general formula (1) on the silicon oxide film.
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier comprising a coating of a gas barrier coating composition comprising at least one selected from the group consisting of a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a metal acylate the film.   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. 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 rate ratio of the gas of the organic silicon compound and the gas containing an oxygen atom is 1 to 3 to 1 pair. The process of forming a silicon oxide film by plasma CVD on a substrate film introduced into the reaction chamber and placed in the reaction chamber in the range of 50, and (a) both ethylene and vinyl on the silicon oxide film after film formation. Polymer and (b) general formula (1)
R ¹ mM (OR ² ) n (1)
(Wherein M is a metal atom, R ¹ is the same or different, an organic group having 1 to 8 carbon atoms, R ² is the same or different, an alkyl group having 1 to 5 carbon atoms or an acyl having 1 to 6 carbon atoms) A metal alcoholate, a hydrolyzate of the metal alcoholate, a metal alcoholate of the metal alcoholate, wherein m and n are each an integer of 0 or more, and m + n is a valence of M. A gas barrier film comprising: a condensate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound, and a gas barrier coating composition containing at least one selected from the group of metal acylates. Production method.   The method for producing a gas barrier film according to claim 8, wherein the silicon oxide film thus formed is subjected to a heat treatment in a temperature range of 50 ° C. to 200 ° C. before applying the gas barrier coating composition.   The method for producing a gas barrier film according to claim 8 or 9, wherein after the gas barrier coating composition is applied, heat treatment is performed for drying the coating film of the gas barrier coating composition and heat treatment of the silicon oxide film. .   The gas barrier film according to any one of claims 8 to 10, wherein a coating film of the gas barrier coating composition is formed using a gas barrier coating composition further containing a nitrogen-containing organic solvent as the gas barrier coating composition. Manufacturing method.   The gas barrier coating composition according to any one of claims 8 to 11, wherein a coating film of the gas barrier coating composition is formed using a gas barrier coating composition further containing inorganic fine particles as the gas barrier coating composition. Method. A gas barrier coating composition was prepared by hydrolyzing the component (b) in water or a mixed solution containing water and a hydrophilic organic solvent, and then mixing the component with the component (a). The method for producing a gas barrier film according to any one of claims 8 to 11, wherein the gas barrier film is applied on a film.

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