JP2009138248A - Raw powder for ion plating evaporation source material, ion plating evaporation source material and method for producing the same, gas barrier sheet and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a raw powder for an ion plating evaporation source material, the raw powder materializing deposition of a gas barrier film having high productivity, excellent gas barrier property, heat resistance and corrosion resistance. <P>SOLUTION: The raw powder contains silicon nitride or silicon oxynitride having a mean particle diameter of ≤5 μm and hexavalent ceramic material having a mean particle diameter of ≤5 μm. In the raw powder, the hexavalent ceramic material is preferably molybdenum oxide and/or molybdenum nitride, and the content of the hexavalent ceramic material is preferably ≥5 pts.wt. and ≤50 pts.wt. to 100 pts.wt. silicon nitride or silicon oxynitride. The ion plating evaporation source material is formed by sintering or granulating the raw powder into lumpy particles having a mean particle diameter of ≥2 mm or lumpy matter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a raw material powder for an ion plating evaporation source material suitable for an ion plating method, an ion source evaporation source material and a manufacturing method thereof, a gas barrier sheet and a manufacturing method thereof, and more specifically, a dense network. And a raw material powder of an evaporation source material for ion plating that can form a gas barrier film having good heat resistance, gas barrier properties, and corrosion resistance.

  As a gas barrier sheet having a barrier property against oxygen gas, water vapor and the like, a sheet in which an inorganic oxide film such as silicon oxide or aluminum oxide is provided as a gas barrier film on a base material has been proposed. Such a gas barrier sheet is excellent in transparency, has almost no influence on the environment, and demand for the packaging material is highly expected.

  As a method for forming a gas barrier film made of an inorganic oxide, an ion plating method is employed in addition to a vacuum vapor deposition method and a sputtering method. The gas barrier film formed by the ion plating method is superior to the deposited film formed by vacuum deposition in terms of adhesion to the substrate and the denseness, and is the same as the sputtered film formed by the sputtering method. There is a feature that it is a degree. On the other hand, the formation of the gas barrier film by the ion plating method is characterized in that it is larger than the sputtering method in terms of film formation speed and is similar to the vacuum deposition method.

As a gas barrier film manufactured by an ion plating method having such characteristics, for example, Patent Document 1 discloses an inorganic nitride thin film and an inorganic nitridation oxide in which a barrier layer (gas barrier film) is formed by hollow cathode ion plating. A transparent barrier film that is one of physical thin films is described. As a specific example of the barrier layer, a nitride such as Si or C (a nitride of carbon silicide or the like) is particularly preferable, and SiN _x (x = 1 to 2) which is a nitride of Si is particularly preferable. It is described that ceramics obtained by appropriately nitriding oxides such as P and Si (SiO _x N _y obtained by nitriding SiO _x that is an oxide of Si, PON that is nitrided oxide of P, and the like) can be mentioned. Yes.
JP 2000-15737 A (Claim 1, paragraph 0019)

  Although silicon nitride and silicon oxynitride used in Patent Document 1 are useful materials having a certain gas barrier property, the present inventors have further studied in order to ensure their practicality. It has been found that it has various problems.

  First, when silicon nitride is to be deposited by ion plating in vacuum, it becomes conductive as its state changes (solid phase → liquid phase (at least locally liquefied) → gas phase). The rate greatly changes, overcurrent, voltage drop, etc. occur, and there is a problem that stable film formation is difficult.

  Moreover, although the gas barrier film made of silicon nitride or silicon oxynitride has a predetermined gas barrier property as described above, in recent years, there has been a demand for higher performance in fields such as display applications, and only oxygen permeability In addition, there is a problem that it is desired to comprehensively improve the gas barrier property by suppressing the water vapor transmission rate. There is also a problem of further improving heat resistance and corrosion resistance.

  The present invention has been made to solve the above-mentioned problems, and its purpose is to provide evaporation for ion plating capable of forming a gas barrier film with high productivity and excellent gas barrier properties, heat resistance, and corrosion resistance. It is to provide a raw material powder of a source material, and more specifically, a raw material powder of an ion plating evaporation source material suitable for an ion plating method, an ion plating evaporation source material and a manufacturing method thereof, a gas barrier sheet, and It is in providing the manufacturing method.

  In the course of conducting research and development for improving gas barrier properties, heat resistance, and corrosion resistance while improving productivity in a gas barrier sheet using silicon nitride or silicon oxynitride as a gas barrier film. The present inventors have found that the gas barrier property is remarkably improved by improving the evaporation source material used in the ion plating method.

  In order to solve the above problems, the raw material powder of the ion source evaporation source material of the present invention comprises silicon nitride or silicon oxynitride having an average particle size of 5 μm or less, and a hexavalent ceramic material having an average particle size of 5 μm or less; It is characterized by having.

  According to the present invention, since the raw material powder has silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less, the raw material powder is sintered or When the granulated evaporation source material is used as an evaporation source for ion plating, evaporation of this evaporation source is facilitated. As a result, productivity is improved and gas barrier properties and heat resistance of the formed gas barrier film are improved. And corrosion resistance are remarkably improved.

  In the raw material powder of the evaporation source material for ion plating of the present invention, the hexavalent ceramic material is preferably molybdenum oxide and / or molybdenum nitride.

  According to the present invention, since the hexavalent ceramic material is molybdenum oxide and / or molybdenum nitride, high-density molybdenum oxide or molybdenum nitride is used while using molybdenum having a low melting point. Evaporation is easy and the gas barrier film is likely to be dense. As a result, productivity is further improved, gas barrier properties of the formed gas barrier film are further improved, and heat resistance and corrosion resistance are further improved. Cheap.

  In the raw material powder of the evaporation source material for ion plating of the present invention, the content of the hexavalent ceramic material is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the silicon nitride or silicon oxynitride. Preferably there is.

  According to this invention, since the content of the hexavalent ceramic material is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride, the significance of containing the hexavalent ceramic material is included. As a result, productivity, gas barrier properties, heat resistance, and corrosion resistance can be improved more easily.

  In order to solve the above problems, a method for producing an ion plating evaporation source material of the present invention includes a step of preparing a raw material powder of the ion plating evaporation source material of the present invention, and granulating or sintering the raw material powder. And a step of processing into a predetermined shape.

  According to this invention, the method includes the steps of preparing a raw material powder of the evaporation source material for ion plating of the present invention and a step of granulating or sintering the raw material powder to process it into a predetermined shape. When the evaporated or granulated evaporation source material is used as an evaporation source for ion plating, evaporation of the evaporation source is facilitated. As a result, productivity is improved and gas barrier properties of the gas barrier film to be formed are improved. , Heat resistance and corrosion resistance are remarkably improved.

  In the method for producing an evaporation source material for ion plating according to the present invention, the step of processing into the predetermined shape includes firing the silicon nitride or the silicon oxynitride constituting the raw material powder and the hexavalent ceramic material. The step is preferably a step in which the particles are granulated or granulated and processed into massive particles or aggregates having an average particle diameter of 2 mm or more.

  According to the present invention, in the step of processing into a predetermined shape, the silicon nitride or silicon oxynitride constituting the raw material powder and the hexavalent ceramic material are sintered or granulated to form a lump having an average particle diameter of 2 mm or more. Since it processes into a particle | grain or a lump, it becomes easy to prevent the scattering at the time of evaporation of the evaporation source material obtained as a result.

  An evaporation source material for ion plating according to the present invention for solving the above-described problems has silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less and a hexavalent ceramic material having an average particle diameter of 5 μm or less. An evaporation source material for ion plating, which is obtained by sintering or granulating raw material powder of an evaporation source material for ion plating, and is made up of massive particles or aggregates having an average particle diameter of 2 mm or more, The evaporation source material is vaporized without passing through the liquid phase when the evaporation source material for heating is heated.

  According to this invention, a raw material powder of an evaporation source material for ion plating having silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less is sintered. Alternatively, an evaporation source material for ion plating made of agglomerated particles or a mass having an average particle diameter of 2 mm or more obtained by granulation, and when the evaporation source material for ion plating is heated, Since vaporization occurs without going through a liquid phase, when this evaporation source material is used as an evaporation source for ion plating, evaporation of the evaporation source is facilitated, and as a result, productivity is improved. The gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved. Although conventional evaporation source materials for ion plating have been studied by vapor deposition material manufacturers, many of them use vacuum evaporation source materials and sputtering target materials as they are, with the aim of improving film quality. In fact, no evaporation source material for ion plating has been proposed.

  In the evaporation source material for ion plating of the present invention, the hexavalent ceramic material is preferably molybdenum oxide and / or molybdenum nitride.

  According to the present invention, since the hexavalent ceramic material is molybdenum oxide and / or molybdenum nitride, high-density molybdenum oxide or molybdenum nitride is used while using molybdenum having a low melting point. Evaporation is easy and the gas barrier film is likely to be dense. As a result, productivity is further improved, gas barrier properties of the formed gas barrier film are further improved, and heat resistance and corrosion resistance are further improved. Cheap.

  In the evaporation source material for ion plating of the present invention, the content of the hexavalent ceramic material is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the silicon nitride or the silicon oxynitride. preferable.

  According to this invention, since the content of the hexavalent ceramic material is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride, the significance of containing the hexavalent ceramic material is included. As a result, productivity, gas barrier properties, heat resistance, and corrosion resistance can be improved more easily.

  The method for producing a gas barrier sheet of the present invention that solves the above-described problem includes an ion plating comprising silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less. A step of preparing an ion plating evaporation source material having a predetermined shape obtained by sintering or granulating raw material powder of an evaporation source material for an ion source, and a substrate on which the ion plating evaporation source material is used as an evaporation source material And a step of forming a gas barrier film by ion plating.

  According to this invention, the step of preparing the ion plating evaporation source material of the present invention, and the ion barrier film formation on the substrate using the ion plating evaporation source material as the evaporation source material. In particular, by using the ion plating evaporation source material of the present invention, when this evaporation source material is used as an evaporation source for ion plating, the evaporation source can be easily evaporated. As a result, productivity is improved and gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved.

  In the method for producing a gas barrier sheet of the present invention, the hexavalent ceramic material is preferably molybdenum oxide and / or molybdenum nitride.

  According to the present invention, since the hexavalent ceramic material is molybdenum oxide and / or molybdenum nitride, high-density molybdenum oxide or molybdenum nitride is used while using molybdenum having a low melting point. Evaporation is easy and the gas barrier film is likely to be dense. As a result, productivity is further improved, gas barrier properties of the formed gas barrier film are further improved, and heat resistance and corrosion resistance are further improved. Cheap.

  In the method for producing a gas barrier sheet of the present invention, the content of the hexavalent ceramic material in the ion plating evaporation source material is 5 parts by weight with respect to 100 parts by weight of the silicon nitride or the silicon oxynitride. The amount is preferably 50 parts by weight or less.

  According to this invention, the content of the hexavalent ceramic material in the evaporation source material for ion plating is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride. The significance of including a hexavalent ceramic material is particularly high, and as a result, productivity, gas barrier properties, heat resistance, and corrosion resistance can be improved more easily.

  The gas barrier sheet of the present invention for solving the above problems is a gas barrier sheet comprising a gas barrier film on at least one surface of a substrate, wherein the gas barrier film has an atomic ratio of Si: N: Mo: O. The Si—N—Mo—O film is in the range of 100: 80 to 120: 1 to 30:70 to 120.

  According to the present invention, the gas barrier film is an Si—N—Mo—O film having a Si: N: Mo: O atomic ratio in the range of 100: 80 to 120: 1 to 30:70 to 120. Thus, a gas barrier sheet having a gas barrier film having a uniform film quality in the thickness direction and a high density can be obtained, and as a result, a gas barrier sheet having significantly improved gas barrier properties, heat resistance, and corrosion resistance can be provided. In addition, the atomic ratio shown by this invention has shown the value in the bulk.

  According to the raw material powder of the ion source evaporation source material of the present invention, when the evaporation source material obtained by sintering or granulating the raw material powder is used as the evaporation source for ion plating, the evaporation source can be easily evaporated. As a result, productivity is improved and gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved.

  According to the method for producing an evaporation source material for ion plating of the present invention, when the evaporated or evaporated evaporation source material is used as an evaporation source for ion plating, evaporation of the evaporation source is facilitated. The productivity is improved, and the gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved.

  According to the evaporation source material for ion plating of the present invention, evaporation of the evaporation source material is facilitated. As a result, productivity is improved and gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be formed are improved. Is significantly improved. In contrast to these ion plating evaporation source materials of the present invention, conventional ion plating evaporation source materials have been studied by vapor deposition material manufacturers, but most of them use vacuum evaporation evaporation source materials and sputtering target materials. The actual situation is that the evaporation source material for ion plating for the purpose of improving the film quality has not been proposed.

  According to the method for producing a gas barrier sheet of the present invention, in particular, the evaporation source material for ion plating of the present invention can be used to facilitate the evaporation of the evaporation source material. The gas barrier property, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved.

  According to the gas barrier sheet of the present invention, a gas barrier sheet having a uniform film quality in the thickness direction and a high density can be obtained. As a result, a gas barrier sheet having significantly improved gas barrier properties, heat resistance, and corrosion resistance is provided. it can.

  Next, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

(Raw material powder of evaporation source material for ion plating)
The raw material powder of the evaporation source material for ion plating of the present invention (in this specification, simply referred to as “raw material powder”) is an evaporation source material used as an evaporation source of atoms to be ionized in the ion plating method. Specifically, it has silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less and a hexavalent ceramic material having an average particle diameter of 5 μm or less. As a result, when the evaporation source material obtained by sintering or granulating the raw material powder is used as an evaporation source for ion plating, evaporation of the evaporation source is facilitated, resulting in improved productivity and film formation. The gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be improved are remarkably improved.

  When the ion plating method is adopted, it is generally attempted to use an evaporation source material having a property of sublimation from the solid phase to the gas phase when plasma is irradiated. This is because, in the case of an evaporation source material that undergoes a phase change from solid phase to liquid phase to gas phase when plasma irradiation is performed, the deposition rate is slowed down by the amount of liquid phase, and the deposition time is lengthened. . Here, according to the study of the present inventor, silicon nitride and silicon oxynitride have the property of causing a phase change from solid phase to liquid phase (at least locally liquefied) → gas phase during plasma irradiation. Since the conductivity changes greatly with the change of state (solid phase → liquid phase (at least locally liquefied) → gas phase), overcurrent, voltage drop, etc. occur and stable It was found that film formation was difficult. Therefore, an evaporation source material obtained by sintering or granulating raw material powder of an ion plating evaporation source material in which hexavalent ceramic material is added to silicon nitride or silicon oxynitride is obtained, and this evaporation source material is ion-plated. As an evaporation source, it has been found that evaporation of the evaporation source is facilitated. As a result, it has been found that the productivity of the gas barrier sheet is improved and the gas barrier property, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved.

The silicon nitride used as a raw material is not particularly limited as long as it is a compound composed of nitrogen and silicon. Specifically, silicon nitride is usually represented by Si ₃ N ₄ and is suitable as a raw material powder of the present invention, in which a conventionally known material can be used. The reason is based on various characteristics of Si ₃ N ₄ , and examples of the characteristics include gas barrier properties, heat resistance, insulation properties, and plasma resistance.

  The silicon oxynitride used as a raw material is not particularly limited as long as it is a compound composed of oxygen, nitrogen, and silicon. Specifically, silicon oxynitride is obtained by various methods such as natural oxidation of silicon nitride, baking and oxidizing silicon nitride, nitriding silicon oxide, and progressing oxidation and nitridation using silicon as a raw material. be able to. Conventionally known silicon oxynitride can be used as the raw material powder of the present invention. The reason is based on various characteristics of silicon oxynitride, and examples of the characteristics include gas barrier properties, heat resistance, insulation properties, and plasma resistance.

  The property of silicon nitride or silicon oxynitride used as a raw material is a powder, and more specifically, a powder having an average particle size of 5 μm or less. Here, in the present invention, the “average particle size” is a result obtained by measuring a predetermined amount (for example, 1 g) of powder with a particle size distribution meter (Coulter counter method). Silicon nitride or silicon oxynitride may contain some impurities and other elements, but usually has a purity of 99.9% or more.

  There is no restriction | limiting in particular as a hexavalent ceramic material. In the present invention, by mixing a hexavalent ceramic material with silicon nitride or silicon oxynitride, an unprecedented gas barrier film having excellent heat resistance, corrosion resistance, and gas barrier properties can be provided. This is thought to be due to the formation of a dense network by mixing hexavalent ceramic materials.

  As the hexavalent ceramic material, molybdenum oxide and / or molybdenum nitride is preferably used. This makes it possible to use molybdenum oxide or molybdenum nitride with high density while using molybdenum with a low melting point, and it is easy to evaporate the evaporation source material and the gas barrier film tends to be dense, and as a result, more productive. In addition, the gas barrier property of the gas barrier film to be formed is further improved, and the heat resistance and corrosion resistance are likely to be further improved.

As described above, when silicon nitride or silicon oxynitride is formed by an ion plating method in a vacuum, the electrical conductivity changes greatly with the state change, so that overcurrent, voltage drop, etc. occur, It was not easy to form a film stably. Therefore, in the present invention, by obtaining an evaporation source for ion plating from a raw material powder containing hexavalent ceramic material (preferably molybdenum oxide and / or molybdenum nitride) in silicon nitride or silicon oxynitride, Evaporation of the evaporation source is facilitated. The use of such a hexavalent ceramic material (preferably molybdenum oxide and / or molybdenum nitride) makes it easy to evaporate the evaporation source because of its melting point. For example, molybdenum is a low melting point (795 ° C.) material. For this reason, since the plasma has a low power and a high vapor pressure, it is presumed that the voltage fluctuation is small and the plasma is stabilized. As a result, evaporation of the evaporation source is facilitated, the film formation rate (deposition rate) on the substrate is increased, the productivity of the gas barrier sheet can be improved, and a dense and highly adherent gas barrier film is obtained. Obtainable. The reason why the gas barrier property of the obtained gas barrier film is improved by using a hexavalent ceramic material (preferably molybdenum oxide and / or molybdenum nitride) is presumed to be its density and valence. For example, molybdenum oxide is a material having a high density of 4.69 g / m ^3, and its valence is hexavalent. For this reason, it is estimated that the network with silicon nitride or silicon oxynitride is stabilized with a dense structure, and as a result, the gas barrier property is improved. Furthermore, the realization of a dense network structure can improve heat resistance and corrosion resistance, and contributes sufficiently to the required performance as a gas barrier sheet for displays that require heat resistance and acid-alkali resistance.

  The property of the hexavalent ceramic material is a powder, and more specifically, a powder having an average particle size of 5 μm or less. The average particle diameter here is also expressed by the result of measurement by the same measurement method as described above. The hexavalent ceramic material may contain some impurities and other elements, but a material having a purity of usually 99.9% or more is used.

  In the raw material powder of the present invention, silicon nitride, silicon oxynitride, and the hexavalent ceramic material have an average particle size of 5 μm or less, preferably 3 μm or less. If a powder material in this range is used, it is easy to mix the powder materials and a raw material powder with reduced dispersion unevenness can be obtained. If such a raw material powder is sintered or granulated to produce an evaporation source material for ion plating, fine silicon nitride powder or silicon oxynitride powder and hexavalent ceramic powder are formed in a small area per unit volume. It exists uniformly, and individual powders can be easily exposed to the plasma generated in the ion plating apparatus.

  The lower limit of the average particle size is not particularly limited, but is preferably 0.2 μm. If the average particle size is 0.2 μm or more, the advantage that the productivity is improved because scattering hardly occurs at the time of mixing powder materials or at the time of sintering / granulation.

  In the raw material powder of the present invention, when the average particle diameter of one or both of silicon nitride or silicon oxynitride and hexavalent ceramic material exceeds 5 μm, dispersion is sufficient even if the powder materials are mixed together Less likely to occur. Therefore, even if the raw material powder obtained is sintered or granulated to produce an evaporation source material for ion plating, a fine silicon nitride powder or silicon oxynitride powder in a small area per unit volume, Since hexavalent ceramic powder does not exist uniformly, stable film formation is difficult.

  The raw material powder of the evaporation source material for ion plating of the present invention is preferably composed mainly of silicon nitride or silicon oxynitride (base material). This is because silicon nitride or silicon oxynitride has a predetermined gas barrier property. In the raw material powder of the evaporation source material for ion plating of the present invention, the gas barrier is realized by ensuring the easiness of evaporation of the evaporation source and improving the productivity, and realizing the dense structure of the network in the gas barrier film. In order to improve the property, heat resistance, and corrosion resistance, a hexavalent ceramic material is used. From such a viewpoint, the content of the hexavalent ceramic material in the raw material powder is usually 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight with respect to 100 parts by weight of silicon nitride or silicon oxynitride. Above, more preferably 20 parts by weight or more, and usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less. The significance of containing a hexavalent ceramic material is particularly significant when an ion source evaporation source material is prepared from a mixed powder containing a hexavalent ceramic material within this range and ion plating is performed using the evaporation source material. As a result, productivity, gas barrier properties, heat resistance, and corrosion resistance can be improved more easily. In particular, when the content of the hexavalent ceramic material is 50 parts by weight or less, evaporation can be performed easily and stably, and a gas barrier film having a dense and good adhesion can be easily obtained.

  When the mass ratio of the hexavalent ceramic material is less than 5 parts by weight, it tends to be insufficient to suppress an overcurrent abnormality during film formation, and a sufficient network structure may not be formed. When it exceeds, the obtained gas barrier film is often colored, for example. For this reason, it is preferable to set it as the said range.

  As explained above, according to the raw material powder of the ion source evaporation source material of the present invention, this raw material powder is sintered or granulated to form an evaporation source material, and this evaporation source material is used as an evaporation source for ion plating. When used as a source, it facilitates evaporation of the evaporation source. As a result, during ion plating film formation, the film formation rate (deposition rate) on the substrate is increased, the productivity of the gas barrier sheet can be improved, and it is dense and has good adhesion and heat resistance. Gas barrier film with excellent heat resistance and corrosion resistance can be obtained.

(Method of manufacturing evaporation source material for ion plating)
The method for producing an evaporation source material for ion plating of the present invention (in the present specification, simply referred to as “evaporation source material production method”) is a process of preparing the raw material powder of the present invention described above. And a process of granulating or sintering the raw material powder into a predetermined shape. As a result, when a sintered or granulated evaporation source material is used as an evaporation source for ion plating, the evaporation source is easily evaporated. As a result, productivity is improved and a gas barrier is formed. The gas barrier properties, heat resistance, and corrosion resistance of the film are significantly improved.

  In the step of preparing the raw material powder, as described in the explanation section of the raw material powder, silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less are used. This is a step of preparing a raw material powder. The raw material powder to be prepared is obtained by mixing silicon nitride or silicon oxynitride powder and hexavalent ceramic material powder by a mixing means such as a mixer.

  The process for processing into a predetermined shape is not particularly limited, but a silicon nitride or silicon oxynitride constituting the raw material powder and a hexavalent ceramic material are sintered or granulated to form a lump with an average particle diameter of 2 mm or more. It is preferably a step of processing into particles or lumps. This makes it easy to prevent scattering of the obtained evaporation source material during evaporation.

  As the sintering means, for example, a general sintering is performed in which the raw material powder is compression-molded into a predetermined shape, and the compression-molded body is heated to a temperature lower than the melting temperature of the constituent powder so that the powders are bonded to each other. Concluding means can be applied. Specifically, various conventionally known methods such as a die press, a CIP press (hydrostatic press), and a RIP press (rubber press) can be applied.

  The sintering temperature is preferably 200 ° C. or higher, more preferably 300 ° C. or higher, preferably 1500 ° C. or lower, more preferably 1000 ° C. or lower, and even more preferably 500 ° C. or lower. By sintering within this range, it is possible to sufficiently degas from the raw material powder, and it is also possible to form massive particles or aggregates having an average particle diameter of 2 mm or more. On the other hand, if the sintering temperature is less than 200 ° C., it may not be sufficiently sintered, and it may not be possible to form a massive particle or mass having an average particle diameter of 2 mm or more. In some cases, silicon is oxidized, and effects such as gas barrier properties disappear. For this reason, it is preferable to sinter in the atmosphere which interrupted oxygen so that silicon nitride etc. may not be oxidized.

  Moreover, as a granulation means, granulation methods, such as stirring granulation, fluidized bed granulation, and extrusion granulation, are applicable. Specifically, the agitation granulation is a method in which raw powder is put in a container, a liquid binder is added to the powder while stirring, the powder is agglomerated, and dried to obtain massive particles close to a sphere. Yes, fluidized bed granulation is a relatively bulky operation in which hot air is blown from the bottom into a container containing raw material powder, the binder is sprayed in a state where the powder is slightly floating in the air, and the powder is agglomerated and dried. Extrusion granulation is a method of obtaining massive particles having relatively high density by an operation of extruding a wet mass of a raw material powder from a small hole into a cylindrical shape and drying it. Such a granulating means usually uses a binder. In such a case, it is common to remove the binder by granulation by heating at, for example, 200 ° C. or higher after granulation. Moreover, when not using a binder, it heat-fires at the arbitrary temperature of 200 degreeC or more and 1500 degrees C or less, for example. By these heating and baking, degassing can be sufficiently performed, and it becomes easy to form massive particles or aggregates having an average particle diameter of 2 mm or more.

  Typical examples of using a binder (binder) when sintering or granulating the raw material powder include starch, wheat protein, cellulose, and the like. I do not care. Such a binder is generally removed by heating and firing after sintering or granulation.

  As described above, according to the method for producing an evaporation source material of the present invention, the granulated or sintered ion plating evaporation source material having a predetermined shape is used as an evaporation source for ion plating. Facilitates evaporation. As a result, during ion plating film formation, the film formation rate (deposition rate) on the substrate is increased, the productivity of the gas barrier sheet can be improved, and it is dense and has good adhesion and heat resistance. Gas barrier film with excellent heat resistance and corrosion resistance can be obtained.

(Evaporation source material for ion plating)
The evaporation source material for ion plating of the present invention is used as an evaporation source of atoms to be ionized in the ion plating method, and is obtained by sintering or granulating the raw material powder of the present invention. is there. Specifically, a raw material powder of an evaporation source material for ion plating having silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less and a hexavalent ceramic material having an average particle diameter of 5 μm or less is sintered or An evaporation source material for ion plating made of agglomerated particles or a mass having an average particle diameter of 2 mm or more obtained by granulation, and when the evaporation source material for ion plating is heated, the evaporation source material Vaporization occurs without going through the liquid phase. This facilitates evaporation of the evaporation source for ion plating. As a result, productivity is improved, and gas barrier properties, heat resistance, and corrosion resistance of the formed gas barrier film are remarkably improved. The explanation about the raw material powder, such as preferably using molybdenum oxide and / or molybdenum nitride as the hexavalent ceramic material, and the explanation about the manufacturing method are as described above. The description in is omitted.

  The evaporation source material may be a block particle or a block product having an average particle diameter of 2 mm or more, and preferably has an average particle diameter of 5 mm or more. The upper limit of the average particle size is not particularly limited. Therefore, it may be a massive particle having a size of about 2 mm, or may be a massive mass having an average particle diameter of 10 m, 50 mm, or the like. The reason why the average particle size is 2 mm or more is that if the particle diameter is less than 2 mm, the particles are fine, and the evaporation source material is likely to scatter due to the impact during the plasma irradiation in the ion plating apparatus. This is because it tends to be time-consuming to handle. The upper limit of the average particle diameter is not particularly limited, but for example, it is about 200 mm. The upper limit of the average particle diameter is not particularly limited as long as it is large enough to be stored in the material input part (hearth) of the vapor deposition apparatus. Further, the form of the particles of the evaporation source material may be round, elliptical, rectangular or the like. Various methods can be applied to the sintering or granulation to obtain a lump or lump. The “average particle size” of the evaporation source material is the result of measuring a predetermined amount (for example, 1 g) of powder with a particle size distribution meter (Coulter counter method), similarly to the average particle size of the raw material powder. .

  The ion source evaporation source material of the present invention is preferably composed mainly of silicon nitride or silicon oxynitride. This is because silicon nitride or silicon oxynitride has a predetermined gas barrier property. The evaporation source material for ion plating of the present invention improves the productivity by ensuring the evaporation of the evaporation source, and realizes a dense network structure in the gas barrier film. In order to improve the property and corrosion resistance, a hexavalent ceramic material is used. From this point of view, the content of the hexavalent ceramic material in the evaporation source material for ion plating is usually 5 parts by weight or more, preferably 10 parts by weight or more, with respect to 100 parts by weight of silicon nitride or silicon oxynitride. The amount is preferably 15 parts by weight or more, more preferably 20 parts by weight or more, and usually 100 parts by weight or less, preferably 70 parts by weight or less, more preferably 50 parts by weight or less. If an evaporation source material for ion plating within this range is produced and ion plating is performed using the evaporation source material, the significance of containing a hexavalent ceramic material is particularly high. As a result, productivity, gas barrier , Heat resistance, and corrosion resistance can be improved more easily. In particular, when the content of the hexavalent ceramic material is 50 parts by weight or less, evaporation can be performed easily and stably, and a gas barrier film having a dense and good adhesion can be easily obtained. In general, the content ratio of silicon nitride or silicon oxynitride in the ion plating evaporation source material and the hexavalent ceramic material reflects the content ratio in the raw material powder.

  When the mass ratio of the hexavalent ceramic material is less than 5 parts by weight, the above-described effect is difficult to occur, and when it exceeds 100 parts by weight, the obtained gas barrier film is colored brown or hardened, for example. There are many. Therefore, when the gas barrier film is formed on a transparent member or when it is desired to ensure the flexibility of the gas barrier sheet, the upper limit of the mass ratio of the hexavalent ceramic material to 100 parts by weight of silicon nitride or silicon oxynitride is set to 100. The weight part may be used.

  As described above, according to the evaporation source material for ion plating of the present invention, when used as an evaporation source for ion plating, evaporation of the evaporation source is facilitated. As a result, during ion plating film formation, the film formation rate (deposition rate) on the substrate is increased, the productivity of the gas barrier sheet can be improved, and it is dense and has good adhesion and heat resistance. Gas barrier film with excellent heat resistance and corrosion resistance can be obtained. Although conventional evaporation source materials for ion plating have been studied by vapor deposition material manufacturers, many of them use vacuum evaporation source materials and sputtering target materials as they are, with the aim of improving film quality. In fact, no evaporation source material for ion plating has been proposed.

(Gas barrier sheet)
FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier sheet of the present invention. As shown in FIG. 1, the gas barrier sheet 1 of the present invention is provided with a gas barrier film 3 on at least one surface on a substrate 2, and the gas barrier film 3 includes silicon nitride or silicon oxynitride, 6 It is formed from molybdenum oxide and / or molybdenum nitride as a valence ceramic material. As described in the explanation of the raw material powder, molybdenum oxide and molybdenum nitride use molybdenum having a relatively low melting point, so that the evaporation source is easily evaporated and the density is relatively high and the valence is high. Since it is hexavalent, there is an advantage that a structure having a dense network with silicon nitride or silicon oxynitride is easily realized. The gas barrier film is preferably composed of silicon nitride and molybdenum oxide as a hexavalent ceramic material.

  More specifically, the gas barrier film 3 is a Si—N—Mo—O film having an Si: N: Mo: O atomic ratio in the range of 100: 80 to 120: 1 to 30:70 to 120. . As a result, a gas barrier sheet having a gas barrier film having a uniform film quality in the thickness direction and a high density can be obtained. As a result, a gas barrier sheet having significantly improved gas barrier properties, heat resistance, and corrosion resistance can be provided.

  The atomic ratio of N in the gas barrier film 3 is preferably 85 or more, more preferably 90 or more, and preferably 110 or less, more preferably 105 or less. Further, the atomic ratio of Mo in the gas barrier film 3 is preferably 3 or more, and preferably 29 or less. Furthermore, the atomic ratio of O in the gas barrier film 3 is preferably 75 or more, more preferably 80 or more, and preferably 115 or less.

  The atomic ratio of each element can be evaluated based on the results obtained with an analyzer such as ESCA. In the present invention, the ESCA is measured by ESCA (manufactured by VG Scientific, UK, model: LAB220i-XL). As the X-ray source, a monochrome AlX ray source having an Ag-3d-5 / 2 peak intensity of 300 Kcps to 1 Mcps and a slit having a diameter of about 1 mm were used. The measurement was performed with the detector set on the normal line of the sample surface used for the measurement, and appropriate charge correction was performed. The analysis after the measurement uses the software Eclipse version 2.1 attached to the above-mentioned ESCA apparatus, and corresponds to the binding energy of Si: 2p, N: 2p, O: 1s, Mo: 3d, C: 1s. Performed using peaks. At this time, the background of Shirley is removed for each peak, and the sensitivity coefficient correction of each element is performed on the peak area (Si = 0.865, N = 1.77, O = 2. 850, Mo = 9.74), and the atomic ratio was determined. About the obtained atomic ratio, the number of Si atoms was set to 100, the number of atoms of N, O, and Mo which are other components was computed, and it was set as the component ratio.

  The gas barrier film 3 mainly functions to block the permeation of gases such as oxygen and water vapor, and the gas barrier film in the present invention exhibits high gas barrier properties. The reason for exhibiting such a high gas barrier property is that the gas barrier film 3 is formed using the above-described ion plating evaporation source material of the present invention, and is higher than the case of using a conventionally known ion plating evaporation source material. This is because the film is formed at a film speed, is dense and dense, and has good adhesion.

  The gas barrier property can be measured with various measuring devices, but the water vapor transmission rate was measured under the condition of 90% Rh at 40 ° C. using PARMATRAN-W 3/31 manufactured by Mocon. On the other hand, the above-mentioned measurement of oxygen gas permeability is performed under the condition of Individual Zero measurement in which OX-TRAN 2/20 manufactured by MOCON is used, temperature is 23 ° C., humidity is 90% RH, and background removal measurement is performed. Measured with

  The thickness of the gas barrier film 3 is usually 5 nm or more, preferably 0.01 μm or more, more preferably 0.02 μm or more, and further preferably 0.05 μm or more. If the thickness of the gas barrier film 3 is within the above range, the above-described excellent oxygen permeability and water vapor permeability can be easily satisfied. In particular, if the thickness of the gas barrier film 3 is 0.05 μm or more (50 nm or more), it is easier to ensure the gas barrier property. The thickness of the gas barrier film 3 is preferably 1 μm or less, more preferably 0.2 μm or less. If the thickness of the gas barrier film 3 is in the above range, the film stress is lowered, and when the substrate 2 is a flexible film, the gas barrier film 3 is less likely to be cracked and the gas barrier property is prevented from being lowered. Furthermore, since the time required for film formation can be reduced, productivity is easily improved.

  When transparency is required for the gas barrier sheet of the present invention, the substrate 2 is preferably a material having a high degree of transparency. Specifically, the light transmittance at 400 nm to 700 nm is 80%. The above gas barrier sheet is preferably applied when used for applications such as display media, illumination, solar cell covers, etc. that require contents to be transmitted such as applications that require light transmission. it can. The light transmittance is used in the same meaning as the total light transmittance. However, since the total light transmittance can be optically adjusted from the film thickness and the refractive index, this numerical value is a guide, but is not necessarily strictly applied.

  In FIG. 1, the gas barrier film 3 is formed on one surface of the substrate 2. However, as another form, the gas barrier film may be formed on both surfaces of the substrate 2. The gas barrier film may be formed on one surface of the substrate 2 via a resin layer, or the gas barrier film may be formed on both surfaces of the substrate 2 via a resin layer. Alternatively, the resin layer and the gas barrier film may be laminated repeatedly two or more times. On the gas barrier film 3, a hard coat layer, a scratch-resistant layer, a conductive layer, an antireflection layer, and the like can be appropriately formed as necessary. Further, the gas barrier film 3 may be multilayered.

  Although the base material 2 is a base material to which the ion plating evaporation source material is attached, it can be used without particular limitation. As the base material 2, a sheet-like or film-like one is mainly used, but a non-flexible substrate or a flexible substrate can be used according to a specific application or purpose. For example, non-flexible substrates such as glass substrates, hard resin substrates, wafers, printed substrates, various cards, resin sheets, etc. may be used. For example, polyethylene terephthalate (PET), polyamide, polyolefin, polyethylene naphthalate (PEN), A flexible substrate such as polycarbonate, polyacrylate, polymethacrylate, polyurethane acrylate, polyethersulfone, polyimide, polysilsesquioxane, polynorbornene, polyetherimide, polyarylate, or cyclic polyolefin may be used. In the case where the substrate 2 is made of a resin, a material having heat resistance of preferably 100 ° C. or higher, particularly preferably 150 ° C. or higher is appropriate.

  Although there is no restriction | limiting in particular also about the thickness of the base material 2, From a viewpoint of a flexibility and a form retainability, it is 6 micrometers or more normally, Preferably it is 12 micrometers or more, Usually, it is set as the range of 400 micrometers or less, Preferably it is 250 micrometers or less.

  The resin layer (not shown) provided between the base material 2 and the gas barrier film 3 is for improving the adhesion between the base material 2 and the gas barrier film 3 and further improving the gas barrier property. In addition, a resin layer (not shown) that covers the gas barrier film 3 functions as a protective film, imparts heat resistance, chemical resistance, and weather resistance to the gas barrier sheet, and even if the gas barrier film 3 has a defect portion. It is for improving the gas barrier property by filling it. Such resin layers include polyamic acid, polyethylene resin, melamine resin, polyurethane resin, polyester resin, polyol resin, polyurea resin, polyazomethine resin, polycarbonate resin, polyacrylate resin, polystyrene resin, polyacrylonitrile (PAN) resin, Commercially available resin material such as polyethylene naphthalate (PEN) resin, curable epoxy resin containing high molecular weight epoxy polymer which is a polymer of bifunctional epoxy resin and bifunctional phenols, and used for the above-mentioned base material It can form by 1 type, or 2 or more types of combinations, such as a resin material to perform. The thickness of the resin layer is preferably set as appropriate depending on the material to be used, but can be set, for example, in the range of 5 nm or more and 500 μm or less.

  Such a resin layer may contain a non-fibrous inorganic filler having an average particle size of 0.8 μm or more and 5 μm or less. Examples of the non-fibrous inorganic filler to be used include aluminum hydroxide, magnesium hydroxide, talc, alumina, magnesia, silica, titanium dioxide, clay, and the like, and in particular, calcined clay is preferably used. Such an inorganic filler can be contained in a range of usually 10% by weight or more, preferably 25% by weight or more, and usually 60% by weight or less, preferably 45% by weight or less of the resin layer.

  As described above, according to the gas barrier sheet of the present invention, since the gas barrier film having a uniform film quality in the thickness direction, a high density, a denseness, and good adhesion can be provided, a gas barrier sheet having excellent gas barrier properties can be provided. The gas barrier sheet of the present invention that exhibits such effects can be applied to various members that require gas barrier properties. For example, it may be used as a part of packaging materials for various foods and drinks, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, electronic parts, etc., and configuration of a liquid crystal display device It may be used as a member.

(Method for producing gas barrier sheet)
The method for producing a gas barrier sheet according to the present invention comprises an evaporation source material for ion plating having silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less and a hexavalent ceramic material having an average particle diameter of 5 μm or less. A step of preparing an ion plating evaporation source material having a predetermined shape formed by sintering or granulating raw material powder, and using this ion plating evaporation source material as an evaporation source material, ionizing a gas barrier film on a substrate. And a plating film forming step. The method for producing a gas barrier sheet according to the present invention facilitates evaporation of the evaporation source when the ion plating evaporation source material of the present invention is used as an evaporation source for ion plating. In addition to the improvement, the gas barrier properties, heat resistance, and corrosion resistance of the gas barrier film to be formed are significantly improved.

  In this manufacturing method, the raw material powder, the evaporation source material, and the gas barrier sheet are as described above. For example, as described above, the hexavalent ceramic material is preferably molybdenum oxide and / or molybdenum nitride. Therefore, in order to avoid duplication of explanation, the explanation is omitted here. Moreover, since the method of sintering or granulating the raw material powder into the evaporation source material is also as already described, the description thereof is omitted here.

  FIG. 2 is a configuration diagram showing an example of an ion plating apparatus, and more specifically, a configuration diagram of a hollow cathode type ion plating apparatus used in an example described later. A hollow cathode type ion plating apparatus 101 shown in FIG. 2 includes a vacuum chamber 102, a supply roll 103a, a take-up roll 103b, a coating drum 104 disposed in the chamber 102, and a vacuum chamber 102 via valves. A vacuum exhaust pump 105 connected, partition plates 109 and 109, a film formation chamber 106 separated from the vacuum chamber 102 by the partition plates 109 and 109, and a crucible disposed in the lower part of the film formation chamber 106 107, an anode magnet 108, a pressure gradient plasma gun 110, a converging coil 111, a sheet magnet 112, a pressure gradient, which are disposed at predetermined positions (in the illustrated example, the right side wall of the film formation chamber) of the film formation chamber 106. For adjusting the supply amount of argon gas to the plasma gun 110 And Lube 113, and a vacuum pump 114 connected through a valve to the film forming chamber 106, a valve 116 for adjusting the supply amount of oxygen gas. As shown in the figure, the supply roll 103a and the take-up roll 103b are equipped with a reverse mechanism, and can be unwound and taken up in both directions.

  Formation of a gas barrier film using such an ion plating apparatus 101 is performed as follows. First, the inside of the vacuum chamber 102 and the film forming chamber 106 is depressurized to a predetermined degree of vacuum by the vacuum exhaust pumps 105 and 114, and then a predetermined flow rate of oxygen gas is introduced into the film forming chamber 106 as necessary to evacuate the vacuum. By controlling the degree of opening and closing of a valve between the pump 114 and the film forming chamber 106, a pressure gradient plasma gun in which the inside of the chamber 106 is maintained at a predetermined pressure, the base film is run, and a predetermined flow rate of argon gas is introduced. 110 is supplied with electric power for plasma generation, the crucible 107 on the anode magnet 108 is focused and irradiated with plasma to evaporate the evaporation source material, ionize the evaporated molecules with high density plasma, A predetermined gas barrier film is formed thereon to obtain a gas barrier sheet.

  The present invention is characterized in that the above-described ion plating evaporation source material of the present invention is used as an evaporation source material. When ion plating film formation is performed using the evaporation source material, the film formation speed (deposition speed) on the substrate increases during ion plating film formation, and the productivity of the gas barrier sheet is improved. In addition, it is possible to obtain a gas barrier film that is dense and has good adhesion and excellent heat resistance and corrosion resistance.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

Example 1
MoO ₃ powder (made by high purity chemical, average particle size: 1 μm) as a hexavalent ceramic material with respect to 100 parts by weight of Si ₃ N ₄ powder (made by high purity chemical, average particle size: 1 μm) as silicon nitride powder ) Was added and mixed to obtain a raw material powder according to the present invention.

  The raw material powder was rotated while dropping a 2% cellulose aqueous solution as a binder into the raw material powder to obtain a spherical body of 5 mmφ. Then, it was put into a baking furnace, held at 400 ° C. for 1 hour to remove the binder and sinter the raw material powder to obtain an evaporation source material for ion plating according to the present invention consisting of a lump having an average particle diameter of 5 mmφ. .

  On the other hand, a plastic film substrate made of 100 μm-thick PEN resin (Q65, manufactured by Teijin DuPont Co., Ltd.) dried at 160 ° C. for 1 hour with a dryer is used as a transparent film substrate, and the pressure gradient ion having the structure shown in FIG. It was set between the supply roll 103a and the take-up roll 103b of the plating apparatus.

Next, the produced evaporation source material was put into a crucible in the hollow cathode type ion plating apparatus shown in FIG. 2 and then evacuated. After the degree of vacuum reached 5 × 10 ⁻⁴ Pa, 15 sccm of argon gas was introduced into the plasma gun, and plasma with a current of 110 A and a voltage of 90 V was generated. Plasma was bent in a predetermined direction by maintaining the inside of the chamber at 1 × 10 ⁻³ Pa and a magnetic force, and the evaporation source material according to the present invention was irradiated. It was confirmed that the evaporation source material in the crucible sublimates well. Ion plating was performed for 30 seconds (evaporation rate: 18.5 nm / min) to deposit on the substrate, thereby obtaining a gas barrier film of SiNMoO having a thickness of 9.25 nm. Note that sccm is an abbreviation for standard cubic centimeter per minute, and the same applies to the following examples and comparative examples.

  The composition of the gas barrier film was Si: N: Mo: O = 100: 93: 4: 81 by ESCA (manufactured by VG Scientific, UK, model: LAB220i-XL) measurement. In this ESCA measurement, as the X-ray source, a monochrome AlX ray source having an Ag-3d-5 / 2 peak intensity of 300 Kcps to 1 Mcps and a slit having a diameter of about 1 mm were used. The measurement was performed with the detector set on the normal line of the sample surface used for the measurement, and appropriate charge correction was performed. The analysis after the measurement uses the software Eclipse version 2.1 attached to the above-mentioned ESCA apparatus, and corresponds to the binding energy of Si: 2p, N: 2p, O: 1s, Mo: 3d, C: 1s. Performed using peaks. At this time, the background of Shirley is removed for each peak, and the sensitivity coefficient correction of each element is performed on the peak area (Si = 0.865, N = 1.77, O = 2. 850, Mo = 9.74), and the atomic ratio was determined. About the obtained atomic ratio, the number of Si atoms was set to 100, the number of atoms of N, O, and Mo which are other components was computed, and it was set as the component ratio.

It was 5.8 * 10 < ^-1 > g / m < ² > / day when the water-vapor-permeation rate was measured as gas barrier property. The water vapor transmission rate was measured at a temperature of 40 ° C. and a humidity of 90% RH using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON). Moreover, when the oxygen transmission rate was measured, it was below the measurement limit. The oxygen gas permeability is measured using an oxygen gas permeability measuring device (OX-TRAN 2/20 manufactured by MOCON) at a temperature of 23 ° C., a humidity of 90% RH, and background removal measurement (Individual Zero). ) Measured under conditions with measurement. The measurement limit of the oxygen gas permeability measuring device is 0.01 cc / m ² / day · atm. Moreover, it was 87.9% when the total light transmittance of 400 nm-700 nm of a gas barrier sheet | seat was measured using the haze meter. These film forming conditions and evaluation results are shown in Table 1. The thickness of the gas barrier film of Example 1 is relatively thin at 9.25 nm. For this reason, the water vapor transmission rate becomes a relatively large value, but the water vapor transmission rate can be further improved by adjusting the thickness of the gas barrier film.

(Example 2)
A gas barrier sheet was formed in the same manner as in Example 1 except that ion plating was performed for 60 seconds (deposition rate: 9.8 nm / min) to obtain a gas barrier film of SiNMoO having a thickness of 9.8 nm. As in Example 1, it was confirmed that the evaporation source material in the crucible sublimates well. When ESCA was measured in the same manner as in Example 1, it was Si: N: Mo: O = 100: 94: 4: 94. Moreover, when the water vapor transmission rate was measured, it was 2.3 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, it was below the measurement limit, and the total light transmittance of the gas barrier sheet was 88. 3%. These film forming conditions and evaluation results are shown in Table 1. The thickness of the gas barrier film of Example 2 is relatively thin at 9.8 nm. For this reason, the water vapor transmission rate becomes a relatively large value, but the water vapor transmission rate can be further improved by adjusting the thickness of the gas barrier film.

(Example 3)
Except that the raw material powder according to the present invention was obtained by setting the content of the MoO ₃ powder to 20 parts by weight, and that the ion plating was performed for 240 seconds (deposition rate: 7.4 nm / min), the same as in Example 1. Thus, a gas barrier sheet was formed to obtain a gas barrier film of SiNMoO having a film thickness of 29.8 nm. As in Example 1, it was confirmed that the evaporation source material in the crucible sublimates well. When ESCA was measured in the same manner as in Example 1, it was Si: N: Mo: O = 100: 96: 11: 104. Moreover, when the water vapor transmission rate was measured, it was 7.3 × 10 ⁻² g / m ² / day. When the oxygen transmission rate was measured, it was below the measurement limit, and the total light transmittance of the gas barrier sheet was 89. It was 1%. These film forming conditions and evaluation results are shown in Table 1.

Example 4
Except that the raw material powder according to the present invention was obtained by setting the content of MoO ₃ powder to 30 parts by weight, and that the ion plating was performed for 240 seconds (deposition rate: 14.4 nm / min), the same as in Example 1. Thus, a gas barrier sheet was formed to obtain a SiNMoO gas barrier film having a thickness of 57.8 nm. As in Example 1, it was confirmed that the evaporation source material in the crucible sublimates well. When ESCA was measured in the same manner as in Example 1, it was Si: N: Mo: O = 100: 102: 14: 106. Moreover, when the water vapor transmission rate was measured, it was 8.2 × 10 ⁻² g / m ² / day. When the oxygen transmission rate was measured, it was below the measurement limit, and the total light transmittance of the gas barrier sheet was 90. 0.7%. These film forming conditions and evaluation results are shown in Table 1.

(Example 5)
A gas barrier was obtained in the same manner as in Example 1 except that the raw material powder according to the present invention was obtained by setting the content of MoO ₃ powder to 50 parts by weight and that the ion plating was performed for 240 seconds (deposition rate: 9 nm / min). Then, a gas barrier film of SiNMoO having a film thickness of 36 nm was obtained. As in Example 1, it was confirmed that the evaporation source material in the crucible sublimates well. When ESCA was measured in the same manner as in Example 1, it was Si: N: Mo: O = 100: 89: 28: 113. Further, when the water vapor transmission rate was measured, it was 1.8 × 10 ⁻⁰ g / m ² / day, and when the oxygen transmission rate was measured, it was 2.74 cc / m ² / day · atm, which is a gas barrier sheet. The total light transmittance was 89.6%. These film forming conditions and evaluation results are shown in Table 1. In the gas barrier film of Example 5, the water vapor transmission rate and the oxygen transmission rate are relatively large, but these characteristics can be further improved by adjusting the thickness of the gas barrier film.

(Comparative Example 1)
An attempt was made to form a gas barrier sheet in the same manner as in Example 1 except that no MoO ₃ powder was used and that ion plating was performed for 30 seconds (deposition rate: 48.4 nm / min). However, when attempting to open the shutter during ion plating, an abnormal voltage drop occurred and the film formation failed. Therefore, the current increased slowly again, but this time an overcurrent abnormality warning occurred. After ignoring the warning, the SiON gas barrier film having a film thickness of 24.2 nm was obtained by attaching to the substrate for 30 seconds. When ESCA was measured in the same manner as in Example 1, it was Si: O: N = 100: 60: 90. Moreover, when the water vapor transmission rate was measured, it was 2.4 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, it was below the measurement limit, and the total light transmittance of the gas barrier sheet was 87. 8%. These film forming conditions and evaluation results are shown in Table 1.

It is a schematic sectional drawing which shows the example of the gas barrier property sheet | seat of this invention. It is a block diagram of the hollow cathode type ion plating apparatus used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gas barrier sheet | seat 2 Base material 3 Gas barrier film | membrane 101 Hollow cathode type ion plating apparatus 102 Vacuum chamber 103a Supply roll 103b Winding roll 104 Coating drum 105 Vacuum exhaust pump 106 Film formation chamber 107 Crucible 108 Anode magnet 109 Partition plate 110 Pressure gradient Type plasma gun 111 Converging coil 112 Sheet magnet 113 Valve 114 Vacuum exhaust pump 116 Valve

Claims (12)

  A raw material powder of an evaporation source material for ion plating, characterized by comprising silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less.   The raw material powder of the evaporation source material for ion plating according to claim 1, wherein the hexavalent ceramic material is molybdenum oxide and / or molybdenum nitride.   The evaporation for ion plating according to claim 1 or 2, wherein the content of the hexavalent ceramic material is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the silicon nitride or the silicon oxynitride. Raw material powder. Preparing a raw material powder of the evaporation source material for ion plating according to any one of claims 1 to 3,
And a step of granulating or sintering the raw material powder to process it into a predetermined shape.   In the step of processing into the predetermined shape, the silicon nitride or the silicon oxynitride constituting the raw material powder and the hexavalent ceramic material are sintered or granulated to form massive particles having an average particle diameter of 2 mm or more. Or the manufacturing method of the evaporation source material for ion plating of Claim 4 which is a process processed into a lump. Obtained by sintering or granulating a raw material powder of an ion source evaporation source material having silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less An ion source evaporation source material consisting of lump particles or lump having an average particle diameter of 2 mm or more,
An evaporation source material for ion plating, wherein when the evaporation source material for ion plating is heated, vaporization of the evaporation source material occurs without going through a liquid phase.   The evaporation source material for ion plating according to claim 6, wherein the hexavalent ceramic material is molybdenum oxide and / or molybdenum nitride.   The evaporation for ion plating according to claim 6 or 7, wherein the content of the hexavalent ceramic material is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the silicon nitride or the silicon oxynitride. Source material. Sintered or granulated raw material powder of an ion source evaporation source material having silicon nitride or silicon oxynitride having an average particle size of 5 μm or less and a hexavalent ceramic material having an average particle size of 5 μm or less Preparing an evaporation source material for ion plating of a predetermined shape;
And a step of ion-plating a gas barrier film on a substrate using the ion-plating evaporation source material as an evaporation source material.   The method for producing a gas barrier sheet according to claim 9, wherein the hexavalent ceramic material is molybdenum oxide and / or molybdenum nitride.   The content of the hexavalent ceramic material in the evaporation source material for ion plating is 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the silicon nitride or the silicon oxynitride. Or the manufacturing method of the gas-barrier sheet of Claim 10. In a gas barrier sheet comprising a gas barrier film on at least one surface on a substrate,
The gas barrier film is a Si—N—Mo—O film having an Si: N: Mo: O atomic ratio of 100: 80 to 120: 1 to 30:70 to 120. Sex sheet.

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