JP5206111B2 - Raw material powder for ion plating evaporation source material, ion plating evaporation source material and manufacturing method thereof, and gas barrier sheet manufacturing method - Google Patents

Description

  The present invention provides a raw material powder of an ion plating evaporation source material suitable for the ion plating method (in this specification, sometimes referred to as “raw material powder”), an ion plating evaporation source material (this specification). In the present invention, it may be referred to as “evaporation source material”) and a production method thereof (in this specification, sometimes referred to as “evaporation source material production method”), a gas barrier sheet and a production method thereof, Specifically, the raw material powder of the evaporation source material for ion plating that can suppress the occurrence of splash of the evaporation source material during ion plating, enables stable film formation, and can form a dense and highly adherent gas barrier film Etc.

  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 either an inorganic nitride thin film or an inorganic nitride oxide thin film in which a barrier layer is formed by hollow cathode ion plating. A transparent barrier film 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) Japanese Patent Laying-Open No. 2004-231979 (claim 1, paragraph 0008, FIG. 1)

  Silicon nitride introduced in Patent Document 1 is a material suitable for forming a dense gas barrier film having a high gas barrier property. However, when an attempt is made to form silicon nitride using the ion plating method, splash during film formation is likely to occur, and thus film defects are likely to occur, and the high gas barrier properties of silicon nitride cannot be fully enjoyed. There are challenges. In addition, silicon nitride has a problem that it is a material unsuitable for an ion plating method in which plasma is irradiated because the electrical characteristics of the surface of the silicon nitride greatly change when the state changes from solid to gas.

  More specifically, since silicon nitride is a sublimation type material, fine scattering occurs during plasma irradiation. And if the scattered fine particle (splash particle) adheres on a base material, it will become a foreign material and a pinhole, and degradation of gas barrier property will arise. Conventionally, as a method of suppressing the formation of pinholes on the substrate by such splash particles, a method of modifying or improving the film forming apparatus side has been employed (for example, Patent Document 2).

  Furthermore, when silicon nitride is sublimated with plasma, current easily flows on the material surface at that moment, leading to a rapid drop in voltage, causing plasma to become unstable, and plasma irradiation is stopped by the power protection circuit. As a result, a phenomenon in which film formation does not proceed easily occurs. Therefore, while silicon nitride has an advantage of excellent gas barrier properties, there is a problem that film formation is difficult by the ion plating method.

  The present invention solves the above-mentioned problems, and its purpose is to form a gas barrier film that suppresses the occurrence of film defects, enables stable film formation, and can fully enjoy the high gas barrier properties of silicon nitride. In particular, it is intended to provide a raw material powder of an evaporation source material for ion plating, and more specifically, a raw material powder of an ion source for evaporation suitable for an ion plating method, an evaporation source material for ion plating and its It is in providing a manufacturing method, a gas barrier sheet, and its manufacturing method.

  In the process of conducting research and development to enable stable film formation and fully enjoy the high gas barrier property of silicon nitride, the present inventor nitridated the raw material powder of the ion source evaporation source material. By adding an appropriate amount of molten material such as silicon oxide together with silicon, it is possible to suppress fine scattering of splash particles by locally melting the plasma irradiation part (creating a semi-molten state) and plasma irradiation. It was found that it can be performed stably. As a result, it has been found that the high gas barrier property inherent to the silicon nitride material can be sufficiently obtained.

  The raw material powder of the evaporation source material for ion plating of the present invention for solving the above problems contains silicon nitride having an average particle size of 5 μm or less and a melt-type material having an average particle size of 5 μm or less, The content of the melt-type 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.

  According to this invention, the silicon nitride having an average particle diameter of 5 μm or less and the molten material having an average particle diameter of 5 μm or less are contained, and the content of the molten material is 100 parts by weight of silicon nitride. Since it is 5 parts by weight or more and 50 parts by weight or less, if the evaporation source material obtained by sintering this raw material powder is used as an evaporation source for ion plating, the occurrence of splash during film formation by the ion plating method is suppressed. It is possible to suppress the rapid change in the electrical resistance of silicon nitride during plasma irradiation, and as a result, the occurrence of film defects is suppressed, enabling stable film formation, and the high gas barrier property of silicon nitride is sufficiently obtained. It is possible to provide a raw material powder of an evaporation source material for ion plating capable of forming a gas barrier film that can be enjoyed.

  In the raw material powder of the evaporation source material for ion plating according to the present invention, the molten material is preferably silicon oxide or silicon oxynitride.

  According to the present invention, since the molten material is silicon oxide or silicon oxynitride, if the evaporation source material obtained by sintering the raw material powder is used as an evaporation source for ion plating, it is locally applied during plasma irradiation. Melting is promoted, and as a result, fine scattering of splash particles can be more effectively suppressed.

  The raw material powder of the evaporation source material for ion plating of the present invention is preferably used as the raw material powder of the vapor deposition source material for pressure gradient ion plating.

  According to the present invention, since the raw material powder of the evaporation source material for ion plating according to the present invention is used as the raw material powder for the evaporation source material for pressure gradient ion plating, the pressure of the plasma generating portion of the plasma gun is increased. Therefore, it can be applied to a process that can be supplied as a more stable and pure plasma source, and as a result, better film formation using the ion plating method can be performed.

  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 sintering the raw material powder. And a step of processing into a predetermined shape.

  According to the present invention, the method includes a step of preparing a raw material powder of the evaporation source material for ion plating according to the present invention, and a step of sintering the raw material powder to process it into a predetermined shape. If it is used as an evaporation source, the occurrence of splash during film formation by ion plating can be suppressed, and a rapid change in electrical resistance of silicon nitride during plasma irradiation can be suppressed. The production of an evaporation source material for ion plating capable of forming a gas barrier film that can suppress the generation, enable stable film formation, and can sufficiently enjoy the high gas barrier property of silicon nitride can be provided. Become.

  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 is preferably a step of sintering the raw material powder and processing into a substantially rectangular parallelepiped shape having a side of 5 mm or more. .

  According to this invention, since the raw material powder is sintered and processed into a substantially rectangular parallelepiped shape with a side of 5 mm or more in the process of processing into a predetermined shape, the evaporation source material for ion plating can be set to a predetermined size. As a result, the irradiated portion at the time of plasma irradiation is fixed, and it becomes easy to prevent scattering at the time of evaporation.

  An evaporation source material for ion plating according to the present invention for solving the above-mentioned problems contains silicon nitride having an average particle size of 5 μm or less and a melt-type material having an average particle size of 5 μm or less, An ion source evaporation source material obtained by sintering a raw material powder having a material content of 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the silicon nitride, 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, the silicon nitride having an average particle diameter of 5 μm or less and the molten material having an average particle diameter of 5 μm or less are contained, and the content of the molten material is 100 parts by weight of silicon nitride. An evaporation source material for ion plating obtained by sintering raw material powder of 5 parts by weight or more and 50 parts by weight or less is used, and when this is heated, evaporation of the evaporation source material occurs without going through a liquid phase. Therefore, it is possible to suppress the occurrence of splash at the time of film formation by the ion plating method, the rapid change in electrical resistance of silicon nitride at the time of plasma irradiation is suppressed, and evaporation with a little energy is possible. Atomic ionization is facilitated. As a result, it is possible to provide an evaporation source material for ion plating that can suppress the occurrence of film defects, enable stable film formation, and can form a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride. it can.

  In the evaporation source material for ion plating according to the present invention, the molten material is preferably silicon oxide or silicon oxynitride.

  According to the present invention, since the molten material is silicon oxide or silicon oxynitride, local melting during plasma irradiation is promoted, and as a result, fine splashing of splash particles can be more effectively suppressed. Will be able to.

  The evaporation source material for ion plating of the present invention is preferably used as a deposition source material for pressure gradient ion plating.

  According to the present invention, since the evaporation source material for ion plating of the present invention is used as a deposition source material for pressure gradient ion plating, a stable pure plasma can be obtained by increasing the pressure of the plasma generation part of the plasma gun. The present invention can be applied to a process that can be supplied as a source, and as a result, better film formation by an ion plating method is possible.

  The evaporation source material for ion plating of the present invention preferably has a substantially rectangular parallelepiped shape with one side of 5 mm or more.

  According to this invention, since the evaporation source material for ion plating according to the present invention has a substantially rectangular parallelepiped shape with one side of 5 mm or more, the evaporation source material for ion plating can be set to a predetermined size. As a result, the irradiated part at the time of plasma irradiation is fixed, and it becomes easy to prevent scattering at the time of evaporation.

  The method for producing a gas barrier sheet of the present invention that solves the above problems includes a step of preparing an evaporation source material for ion plating of the present invention, and a substrate using the evaporation source material for ion plating as an evaporation source material. And a step of forming an ion plating film on the gas barrier film.

  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 Therefore, it is possible to suppress the occurrence of splash at the time of film formation by the ion plating method, and a rapid change in electrical resistance of silicon nitride at the time of plasma irradiation is suppressed. Occurrence is suppressed, stable film formation is possible, and a method for producing a gas barrier sheet capable of forming a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride can be provided.

  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 base material, wherein the gas barrier film has an Si: O: N atomic ratio of 100: A Si—O—N film in a range of 50 to 150: 40 to 100, wherein the atomic ratio is uniform in the thickness direction of the gas barrier film.

  According to the present invention, the gas barrier film is a Si—O—N film having an Si: O: N atomic ratio of 100: 50 to 150: 40 to 100, wherein the atomic ratio is the gas barrier. Since it is uniform in the thickness direction of the film (variation is within ± 10%), it has a gas barrier film with a uniform film quality in the thickness direction, and a gas barrier sheet in which defects due to splash are suppressed, resulting in film defects. The gas barrier sheet | seat which generation | occurrence | production of this is suppressed and can fully enjoy the high gas barrier property which silicon nitride has 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 evaporation source material for ion plating of the present invention, generation of film defects is suppressed, stable film formation is possible, and a gas barrier film that can fully enjoy the high gas barrier property of silicon nitride is formed. It is possible to provide a raw material powder of a possible ion plating evaporation source material.

  According to the method for producing an evaporation source material for ion plating of the present invention, the occurrence of film defects is suppressed, stable film formation is possible, and a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride is formed. It is possible to provide a method for producing a possible ion plating evaporation source material.

  According to the evaporation source material for ion plating of the present invention, generation of film defects is suppressed, stable film formation is possible, and a gas barrier film that can fully enjoy the high gas barrier property of silicon nitride can be formed. In addition, it is possible to provide an evaporation source material for ion plating that can increase the film formation rate (deposition rate) by increasing the ionization rate.

  According to the method for producing a gas barrier sheet of the present invention, it is possible to provide a method for producing a gas barrier sheet capable of forming a gas barrier film in which generation of film defects is suppressed and a high gas barrier property of silicon nitride can be fully enjoyed. Can do.

  According to the gas barrier sheet of the present invention, it is possible to provide a gas barrier sheet in which the occurrence of film defects is suppressed and the high gas barrier property of silicon nitride can be fully enjoyed.

  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 according to the present invention is a raw material of an evaporation source material used as an evaporation source of atoms to be ionized in the ion plating method, and specifically has an average particle size of 5 μm or less. A raw material containing silicon nitride and a melt-type material having an average particle size of 5 μm or less, wherein the content of the melt-type material is 5 to 50 parts by weight with respect to 100 parts by weight of silicon nitride It is a powder.

  If the evaporation source material obtained by sintering this raw material powder is used as an evaporation source for ion plating, it is possible to suppress the occurrence of splash during film formation by the ion plating method, and the rapid growth of silicon nitride during plasma irradiation. For ion plating, the change in electrical resistance is suppressed. As a result, the generation of film defects is suppressed, stable film formation is possible, and a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride can be formed. A raw material powder of the evaporation source material can be provided.

That is, when the present inventor examined, since silicon nitride (typically Si ₃ N ₄ ) is a sublimation type material, fine scattering occurs during plasma irradiation, and the scattered particles (splash particles) are the base material. It has been found that the gas barrier property deteriorates due to foreign matters and pinholes adhering to the upper surface, pinholes being formed in the gas barrier film, and flatness of the gas barrier film being lowered. Therefore, despite the fact that silicon nitride itself is a dense material with high gas barrier properties, it is not possible to fully enjoy the benefits of using silicon nitride due to the deterioration of gas barrier properties due to the adhesion of the splash particles onto the substrate. It is a fact. Therefore, by adding a melt-type material (melt-type material) to silicon nitride, the evaporation source material is made semi-meltable and has a viscosity, thereby suppressing the occurrence of splash. However, in order to surely enjoy the original high gas barrier property of silicon nitride, the content of the melt-type material is set within a certain range in order to ensure the denseness of silicon nitride.

Furthermore, as a result of studies by the present inventors, silicon nitride (typically Si ₃ N ₄ ) is irradiated with plasma because the electrical characteristics of the material surface greatly change when the state changes from solid to gas. It was found that the material is not suitable for the ion plating method. More specifically, when silicon nitride is sublimated with plasma, current easily flows on the surface of the material at that moment, leading to a sudden drop in voltage, which makes the plasma unstable, and the power supply protection circuit causes the plasma to become unstable. Is stopped and film formation does not proceed. Therefore, in order to suppress a sudden change in electrical resistance of silicon nitride during the plasma irradiation and perform stable film formation, an appropriate amount of molten material is added to silicon nitride.

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 Si _a N _b (where a is in the range of 2.8 to 3.2 and b is in the range of 3.8 to 4.2. ₃ N ₄ ) and is suitable as a raw material powder of the present invention. The reason is based on various characteristics of Si ₃ N ₄ , and examples of the characteristics include gas barrier properties, heat resistance, and insulation properties. Silicon nitride is in the form of a powder, 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 may contain some impurities and other elements, but usually has a purity of 99.9% or more. Furthermore, silicon nitride may be partially oxidized. For example, silicon nitride partially oxidized by natural oxidation or oxidation during baking may be used.

The melt-type material used as the raw material is not particularly limited as long as the vapor deposition raw material can be made semi-meltable, but is preferably silicon oxide or silicon oxynitride. Among these, silicon oxide is more preferable from the viewpoint of imparting appropriate semi-meltability to the vapor deposition source material. Silicon oxide is a silicon dioxide-based material, more specifically SiO _x (where x is in the range of 1.8 to 2.2) from the viewpoint of ensuring the semi-meltability of the evaporation source material more reliably. And is usually most preferably represented by SiO ₂ .

  The property of the melt-type material is 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 molten material may contain some impurities and other elements, but a material having a purity of usually 99.9% or more is used.

  The content of the melt-type material in the raw material powder is 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of silicon nitride. Within this range, it is possible to form a stable film while suppressing the occurrence of splash during film formation by the ion plating method, and to enjoy the high gas barrier property of silicon nitride itself.

  In the raw material powder of the present invention, the average particle diameter of silicon nitride and the average particle diameter of the melt-type material are both 5 μm or less, preferably 3 μm or less. If silicon nitride and a melt-type material within this range are used, the powder materials can be easily mixed with each other, and a raw material powder having no dispersion unevenness can be obtained. Sintering these raw material powders to produce an evaporation source material for ion plating makes it easy for fine silicon nitride and fine molten material to exist uniformly in a small area per unit volume. Can easily be exposed to the plasma generated in the ion plating apparatus. In particular, in the evaporation source material, a melt-type material exists so as to be uniformly mixed in the silicon nitride, and the action of the melt-type material causes the evaporation source material to exhibit a good semi-melting property, resulting in a splash. It becomes easy to perform stable film formation by suppressing the occurrence of the occurrence and the rapid change in electric resistance, and it becomes easy to enjoy the high gas barrier property of silicon nitride itself.

  The lower limit of the average particle size is not particularly limited, but is preferably 0.2 μm. When 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.

  On the other hand, when the average particle diameter of one or both of silicon nitride and the melt-type material exceeds 5 μm, dispersion hardly occurs even if the powder materials are mixed. Therefore, even when the obtained raw material powder is sintered to produce an evaporation source material for ion plating, fine silicon nitride and molten material are uniformly present in a small area per unit volume. It becomes difficult to obtain the action of the melt-type material causing the above-described sublimation phenomenon, and it becomes difficult to obtain the semi-melting property as the average particle size increases.

  The raw material powder is preferably used as a raw material powder of a vapor deposition source material for pressure gradient ion plating. This makes it possible to apply to a process that can be supplied as a stable and pure plasma source by increasing the pressure of the plasma generation part of the plasma gun. A membrane is possible.

  As described above, according to the raw material powder of the evaporation source material for ion plating of the present invention, this raw material powder is sintered into an evaporation source material, and this evaporation source material is used as an evaporation source for ion plating. Therefore, the occurrence of film defects is suppressed, stable film formation is possible, and a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride can be formed.

In the ion plating method, conventionally, a conductive material has been mainly used as the evaporation source material because of the relationship of using a mechanism of irradiating the plasma to evaporate the evaporation source material. This is because if an insulating material is used as the evaporation source material, the irradiated plasma escapes to the housing of the apparatus and sufficient plasma irradiation cannot be performed on the insulating material. Actually, in Example 1 of Patent Document 1, a barrier layer of SiN _x (x = 4/3) is formed on a base film by an ion plating method. As an example, a Si ingot having a purity of 98% or Si particles having a particle diameter of 2 to 5 mm is used, and nitrogen gas is introduced into the system (N ₂ = 40 sccm) (see paragraphs 0053 and 0054 of Patent Document 1). ).

  In this regard, a technique of using a feedback electrode in the ion plating method has been developed (Japanese Patent Laid-Open No. 11-269636), and an insulating material can be actively used as an evaporation source material. However, as described above, silicon nitride has a sublimation property, which causes a sudden drop in voltage, which prevents plasma from being stably irradiated, and is a material unsuitable for ion plating. Therefore, in the present invention, silicon nitride can be favorably applied to the ion plating method by making the evaporation source material semi-meltable using a melt-type material.

(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 the raw material powder of the present invention. Specifically, it contains silicon nitride having an average particle size of 5 μm or less and a melt type material having an average particle size of 5 μm or less, and the content of the melt type material is 100 parts by weight of silicon nitride. An evaporation source material for ion plating obtained by sintering raw material powder that is 5 parts by weight or more and 50 parts by weight or less, and when the evaporation source material for ion plating is heated, the evaporation source material is vaporized. It is configured to occur without going through a liquid phase. As a result, it is possible to suppress the occurrence of splash during film formation by the ion plating method, to suppress a rapid change in the electrical resistance of silicon nitride during plasma irradiation, and to allow evaporation with little energy. It becomes easy to ionize the atoms. As a result, it is possible to provide an evaporation source material for ion plating that can suppress the occurrence of film defects, enable stable film formation, and can form a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride. it can.

  The evaporation source material is obtained by sintering the raw material powder of the present invention, and the details of the raw material powder are as described above. For example, the above-described molten material is preferably silicon oxide or silicon oxynitride. Thereby, the local melting at the time of plasma irradiation is promoted, and as a result, the fine scattering of the splash particles can be more effectively suppressed. The evaporation source material is preferably used as an evaporation source material for pressure gradient ion plating. This makes it possible to apply to a process that can be supplied as a stable and pure plasma source by increasing the pressure of the plasma generation part of the plasma gun. A membrane is possible. Details of these points have already been described in the above description of the raw material powder, and thus description thereof is omitted to avoid duplication of description. The details of the sintering of the raw material powder will be described in the description of the evaporation source material manufacturing method described later.

  The evaporation source material preferably has a substantially rectangular parallelepiped shape with one side of 5 mm or more. As a result, the ion plating evaporation source material can be set to a predetermined size, and as a result, the irradiated portion at the time of plasma irradiation is fixed, and scattering during evaporation is easily prevented. The shape of the evaporation source material may be a substantially rectangular parallelepiped, that is, a shape similar to a rectangular parallelepiped, and does not have to be a complete rectangular parallelepiped. For example, some corners may be missing. The evaporation source material preferably has at least one side of a substantially rectangular parallelepiped bottom surface of 10 mm or more, more preferably 20 mm or more, and particularly preferably 25 mm or more. By making the evaporation source material into such a flat, substantially rectangular parallelepiped shape, scattering during evaporation can be more effectively suppressed. Moreover, although the upper limit of the length of one side of a substantially rectangular parallelepiped is not specifically limited, For example, it is about 200 mm. The upper limit of the length of one side 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.

  The content of the melt-type material with respect to silicon nitride in the evaporation source material usually reflects the mixing ratio in the raw material powder. Therefore, the content of the melt-type material in the evaporation source material is usually 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and usually 50 parts by weight with respect to 100 parts by weight of silicon nitride. Part or less. Within this range, it is possible to form a stable film while suppressing the occurrence of splash during film formation by the ion plating method, and to enjoy the high gas barrier property of silicon nitride itself. As described above, normally, the composition of the evaporation source material reflects the composition of the raw material powder. However, as described in the explanation of the method of manufacturing the evaporation source material described later, the evaporation source material is sintered. The composition of the obtained evaporation source material may be adjusted by performing an operation such as in an oxygen atmosphere.

  As described above, the evaporation source material for ion plating according to the present invention is composed of silicon nitride and an appropriate amount of melt-type material, and when this is heated, evaporation of the evaporation source material occurs without going through a liquid phase. For this reason, while the sublimation-type material silicon nitride sublimates, the splash-type material and the rapid change in electrical resistance during plasma irradiation are suppressed by the molten material contained in an appropriate amount, and the sublimation property Since the properties are maintained, evaporation with a small amount of energy is possible, and ionization of the evaporated atoms becomes easy. As a result, it is possible to provide an evaporation source material for ion plating that can suppress the occurrence of film defects, enable stable film formation, and can form a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride. it can.

  As described in the explanation of the raw material powder, in the ion plating method, an insulating material can be actively used as an evaporation source material by developing a device using a feedback electrode. As a result, there has been opened a way to satisfactorily form a film by an ion plating method for silicon nitride which is an insulating material while having a high gas barrier property. However, since silicon nitride has a sublimation property, a sudden voltage drop occurs during plasma irradiation, making it difficult to perform stable plasma irradiation, and occurrence of splash is observed. In order to perform good film formation by the coating method, it was necessary to further improve the evaporation source material. In this regard, in the present invention, the evaporation source material is made semi-meltable by using a melt-type material, so that film formation by the ion plating method is good even when silicon nitride is used as the evaporation source material. To be able to.

(Method of manufacturing evaporation source material for ion plating)
The method for producing an evaporation source material for ion plating of the present invention includes a step of preparing the raw material powder of the present invention described above, and a step of sintering the raw material powder and processing it into a predetermined shape. . If the evaporation source material obtained in this way is used as an evaporation source for ion plating, the occurrence of splash during film formation by the ion plating method can be suppressed, and a sudden change in electrical resistance of silicon nitride during plasma irradiation As a result, the occurrence of film defects is suppressed, stable film formation is possible, and a gas barrier film capable of fully enjoying the high gas barrier property of silicon nitride can be formed. A manufacturing method can be provided.

  The step of preparing the raw material powder includes silicon nitride having an average particle size of 5 μm or less and a melt-type material having an average particle size of 5 μm or less, as described in the explanation section of the raw material powder. This is a step of preparing a raw material powder having a melt-type material content of 5 to 50 parts by weight with respect to 100 parts by weight of silicon nitride. The raw material powder to be prepared is, for example, a raw material powder in which the molten material is contained in an amount of 5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of silicon nitride, for example, mixed by mixing means such as a mixer. Is.

  The step of processing into a predetermined shape is not particularly limited, but is preferably a step of sintering the raw material powder and processing it into a substantially rectangular parallelepiped shape with one side of 5 mm or more. As a result, the ion plating evaporation source material can be set to a predetermined size, and as a result, the irradiated portion at the time of plasma irradiation is fixed, and scattering during evaporation is easily prevented.

  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 400 ° C. or higher, and preferably 1500 ° C. or lower, more preferably 1200 ° C. or lower. By sintering within this range, degassing from the raw material powder can be sufficiently performed, and it becomes easy to process into a substantially rectangular parallelepiped shape with one side of 5 mm or more. On the other hand, if the sintering temperature is less than 200 ° C., it becomes difficult to perform sufficient sintering. On the other hand, if the sintering temperature exceeds 1500 ° C., it may be easily oxidized by leaked oxygen when the atmosphere is a non-reactive gas such as Ar or nitrogen.

  The atmosphere at the time of sintering may be appropriately selected according to the composition desired for the evaporation source material. Usually, a non-reactive gas such as Ar or nitrogen is used, but the degree of oxidation of the evaporation source material obtained by adding oxygen to the atmosphere can also be adjusted. On the other hand, when suppressing the reaction between the raw material powder of the evaporation source material and oxygen in the atmosphere during sintering, the above-described non-reactive gas may be used, and the sintering temperature can be arbitrarily set. . On the other hand, when oxygen is contained in the atmosphere (for example, when sintering is performed in the air), the oxidation temperature may be suppressed by setting the sintering temperature low. In this case, the sintering temperature is preferably 1000 ° C. or lower, more preferably 500 ° C. or lower.

  The composition of the gas barrier film of the gas barrier sheet is a Si—O—N film having an Si: O: N atomic ratio in the range of 100: 50 to 150: 40 to 100, and the atomic ratio is the thickness of the gas barrier film. When uniform in the direction, it is preferable to obtain the evaporation source material by the following manufacturing method. First, in order to make the composition in the evaporation source material uniform, for example, a method of mixing a powder of a molten material with a powder of silicon nitride can be mentioned. In addition, a method of adjusting the composition of the evaporation source material by causing the oxidation reaction by sintering the raw material powder in an atmosphere containing oxygen is also effective. The sintering temperature is preferably higher than 1000 ° C, more preferably 1500 ° C or higher.

  The sintering time is not particularly limited, and is usually 0.5 hours or longer and 48 hours or shorter. The sintering time may be appropriately adjusted according to the size of the evaporation source material to be obtained (tablet size) and the sintering temperature.

  In the case of using a binder (binder) when sintering the raw material powder, typical examples thereof include starch, wheat protein, cellulose, etc. I do not care. Such a binder is generally removed by heating and firing after sintering.

  As described above, if the evaporation source material obtained by the evaporation source material manufacturing method of the present invention is used as an evaporation source for ion plating, it is possible to suppress the occurrence of splash at the time of film formation by the ion plating method. A rapid change in electrical resistance of silicon nitride during irradiation is suppressed, and as a result, generation of film defects is suppressed, stable film formation is possible, and a gas barrier film that can sufficiently enjoy the high gas barrier properties of silicon nitride is provided. It is possible to provide a method of manufacturing a deposition source material for ion plating that can be formed into a film.

  In addition, the development of a device using a feedback electrode opened the way to successfully deposit silicon nitride, which is an insulating material, by ion plating. However, silicon nitride can still be used as an evaporation source for ion plating. It was difficult to use the material as it was. Therefore, in the present invention, silicon nitride can be satisfactorily used as an evaporation source material for ion plating by producing an evaporation source material by containing an appropriate amount of a melt-type material in silicon nitride. Details of these points are the same as those already described in the explanation column of the raw material powder and the explanation column of the evaporation source material.

(Gas barrier sheet)
The gas barrier sheet of the present invention is provided with a gas barrier film on at least one surface on a substrate, and the gas barrier film contains silicon nitride and silicon oxide or silicon oxynitride which is preferable as a molten material. Is done. More specifically, the gas barrier film is a Si—O—N film having a Si: O: N atomic ratio in the range of 100: 50 to 150: 40 to 100, and the atomic ratio is a gas barrier film. It is uniform in the thickness direction (variation is within ± 10%). As a result, a gas barrier sheet having a gas barrier film with a uniform film quality in the thickness direction and defects caused by splash is suppressed, and as a result, the occurrence of film defects is suppressed and the high gas barrier property of silicon nitride is sufficiently obtained. A gas barrier sheet that can be enjoyed can be provided. In addition, the atomic ratio shown by this invention has shown the value in the bulk.

The gas barrier film mainly functions to block the permeation of gases such as oxygen and water vapor. The gas barrier film of the present invention has an oxygen permeability of 1 cc / m ² / day · atm or less and a water vapor permeability of 1 g. A high gas barrier property of / m ² / day or less is exhibited. The reason why such a high gas barrier property is exhibited is that the gas barrier film is formed using the above-described evaporation source material for ion plating of the present invention, is stably formed, has few defects, is dense and dense, and has high adhesion. Because it is good.

  The thickness of the gas barrier film is preferably 0.01 μm or more, more preferably 0.02 μm or more. If the thickness of the gas barrier film is within the above range, the above-described excellent oxygen permeability and water vapor permeability can be easily satisfied. The thickness of the gas barrier film is preferably 1 μm or less, more preferably 0.2 μm or less. When the thickness of the gas barrier film is within the above range, the film stress is lowered, and when the base material is a flexible film, the gas barrier film is less likely to be cracked, and the gas barrier property is prevented from being lowered. Therefore, productivity can be easily improved.

  In the present invention, “the atomic ratio is uniform in the thickness direction” means that the variation in the atomic ratio in the thickness direction of the gas barrier film is within ± 10%, preferably within ± 5%. . Such a range of variation is characteristically obtained when the evaporation source material for ion plating of the present invention is used. That is, since the evaporation source material of the present invention is formed by sintering raw material powder obtained by mixing silicon nitride and silicon oxide or silicon oxynitride which is preferable as a melt-type material, the evaporation source material is used. When the ion plating film is formed, the formed gas barrier film is formed almost uniformly in the thickness direction with the above-mentioned atomic ratio (the variation is within ± 10%, preferably within ± 5%). The In addition, the atomic ratio shown in the present invention indicates a value in a bulk, a natural oxide film may be generated on the film surface, and oxidation with a gas component from the base material may proceed at the interface with the base material. In any case, it is considered that the composition is shifted.

  The atomic ratio at this time can be evaluated by the result obtained by 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 software Eclipse version 2.1 attached to the above-mentioned ESCA apparatus, and uses peaks corresponding to binding energies of Si: 2p, N: 1s, C: 1s, and O: 1s. went. At this time, Shirley background is removed for each peak, and sensitivity coefficient correction of each element is performed on the peak area (N = 1.770, Si = 0.865, O = 2. 850) 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 O and N which are other components was calculated, and it was set as the component ratio.

The gas barrier property of the gas barrier film can be estimated from the range of infrared absorption by the Si—N—Si stretching vibration and the film density. Specifically, the Si—O—N film, which is the obtained gas barrier film, has infrared absorption by Si—N—Si stretching vibration in the range of 830 to 1060 cm ⁻¹ , and the film density is preferably 2. The range is 2 g / cm ³ or more, more preferably 2.5 g / cm ³ or more, and preferably 4.0 g / cm ³ or less. If the atomic ratio of the gas barrier film, the infrared absorption band due to Si—N—Si stretching vibration, and the film density are within the above ranges, it is easy to ensure the denseness of the gas barrier film, and high gas barrier properties (oxygen permeability is 1 cc / m ² / day · atm or less, and the water vapor transmission rate is about 1 g / m ² / day or less), and the flexibility of the gas barrier film is easily secured and the durability tends to be high.

  In the present invention, the infrared absorption band due to Si-N-Si stretching vibration is obtained by using a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation, Herschel FT-IR-610) equipped with a multiple reflection (ATR) measuring device. Use to measure. The film density is measured with an X-ray reflectivity measuring device (manufactured by Rigaku Corporation, ATX-E). The gas barrier property can be measured with various measuring devices, and the gas barrier property is measured using PARMATRAN 3/31 manufactured by Mocon under the conditions of 37.8 ° C. and 100% RH.

  When transparency is required for the gas barrier sheet of the present invention, the substrate is preferably a material having a high degree of transparency. Specifically, the light transmittance at 400 nm to 700 nm is 80% or more. The gas barrier sheet is used for applications that require light transmission, such as display media, lighting, and solar cell covers, and applications that require viewing of contents such as packaging and containers. For example, it can be preferably applied. On the other hand, when the gas barrier sheet is used for applications that do not require transparency as described above, it may be a gas barrier sheet having a light transmittance of about 50%, and other applications as a general gas barrier sheet. Can be used. 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.

  As another form of the gas barrier sheet, a gas barrier film may be formed on both surfaces of the substrate, or a gas barrier film may be formed on one surface of the substrate via a resin layer. The gas barrier film may be formed on both surfaces of the base material via the resin layer, or the resin layer and the gas barrier film may be repeatedly laminated twice or more. Good. On the gas barrier film, 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 may be multilayered.

  Although a base material is a base material to which the evaporation source material for ion plating is made to adhere, it can be used without particular limitation. As the substrate, a sheet or film 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. When the substrate is made of a resin, those having a heat resistance of preferably 100 ° C. or higher, particularly preferably 150 ° C. or higher are appropriate.

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

  The resin layer provided between the base material and the gas barrier film is for improving the adhesion between the base material and the gas barrier film and further improving the gas barrier property. The resin layer covering the gas barrier film functions as a protective film, and is for imparting heat resistance, chemical resistance, and weather resistance to the gas barrier sheet. Such resin layers include polyamic acid, polyethylene resin, melamine resin, polyurethane resin, polyester resin, polyol resin, polyurea resin, polyazomethine resin, polycarbonate resin, poly (meth) acrylate resin, polystyrene resin, polyacrylonitrile (PAN). ) Resin, a commercially available resin material such as polyethylene naphthalate (PEN) resin, a curable epoxy resin containing a high molecular weight epoxy polymer that is a polymer of a bifunctional epoxy resin and a bifunctional phenol, and the group described above It can form by 1 type, or 2 or more types of combinations, such as the resin material used for a material. 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 atomic ratio is uniform in the thickness direction of the gas barrier film (variation is within ± 10%), the gas barrier property having a gas barrier film having a uniform film quality in the thickness direction. Can provide a sheet. More specifically, since the gas barrier film having a uniform film quality in the thickness direction, a high density, a denseness, and good adhesion is 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 (food), chemicals such as adhesives and pressure-sensitive adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and electronic parts, and liquid crystal displays. You may use as a structural member of an apparatus. Among these, it is preferable to use in the food field from the viewpoint that low cost is required.

(Method for producing gas barrier sheet)
The method for producing a gas barrier sheet of the present invention comprises a step of preparing the ion plating evaporation source material of the present invention and a gas barrier film on the substrate using the ion plating evaporation source material as an evaporation source material. And a film forming step. By using the evaporation source material of the present invention, it is possible to suppress the occurrence of splash at the time of film formation by the ion plating method, the rapid change in electrical resistance of silicon nitride during plasma irradiation is suppressed, as a result, Occurrence of film defects can be suppressed, stable film formation can be performed, and a method for producing a gas barrier sheet capable of forming a gas barrier film that can fully enjoy the high gas barrier properties of silicon nitride can be provided.

  In this production method, each of the raw material powder, the evaporation source material, the production method of the evaporation source material, and an example of a preferable gas barrier sheet is as described above. For example, the step of preparing the evaporation source material for ion plating according to the present invention may be performed by sintering the raw material powder to prepare the evaporation source material, as described in the explanation of the method for manufacturing the evaporation source material. is there. Therefore, in order to avoid duplication of explanation, the explanation is omitted here.

  Ion plating film formation (ion plating method) in the process of ion plating film formation of a gas barrier film on a substrate is a method of exciting and evaporating evaporates by applying plasma energy during the film formation process in vacuum deposition. A system that promotes ionization. Among these ion plating methods, pressure gradient ion plating is preferable, which is a process that can be supplied as a stable and pure plasma source by increasing the pressure of the plasma generation part of the plasma gun. It is. It is further preferable to use a process including a return electrode so that the current applied to the hearth can be stably returned to the plasma gun.

  When the ion plating method is adopted, since the energy of plasma is large, silicon nitride is partially separated by plasma irradiation, and the gas barrier film has a large amount of metal from which silicon is isolated. May be a film. In such a case, nitrogen gas is introduced into the isolated silicon vapor, and the silicon vapor reacts with the nitrogen gas, so that even if silicon oxide is added, an oxynitride film having a high nitrogen content, that is, having a high gas barrier property. Film can be obtained. In addition to these methods, a method of reacting with oxygen during plasma irradiation by allowing oxygen to exist in the vacuum chamber during vacuum film formation can also be used.

  FIG. 1 is a configuration diagram showing an example of an ion plating apparatus, and more specifically, is a configuration diagram of a hollow cathode type ion plating apparatus used in examples described later. A hollow cathode type ion plating apparatus 101 shown in FIG. 1 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 such as an 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 evacuation pumps 105 and 114, and then a predetermined flow rate of oxygen gas or the like is introduced into the film forming chamber 106 as necessary. By controlling the degree of opening and closing of a valve between the exhaust pump 114 and the film forming chamber 106, the inside of the chamber 106 is maintained at a predetermined pressure, the base film is run, and a pressure gradient plasma in which a predetermined flow rate of argon gas is introduced. Electric power for plasma generation is applied to the gun 110, the plasma flow is converged and irradiated on the crucible 107 on the anode magnet 108 to evaporate the evaporation source material, and the evaporated molecules are ionized by the high-density plasma. A predetermined gas barrier film is formed on the material to obtain a gas barrier sheet.

  FIG. 1 shows an example of an ion plating apparatus. However, as described above, a preferable ion plating apparatus includes a return electrode so that the current applied to the hearth can be stably returned to the plasma gun. is there. As such an apparatus, as described in JP-A No. 11-269636, an insulating tube that surrounds the periphery of the plasma beam at the plasma beam irradiation exit of the plasma gun and protrudes in an electrically floating state, What is necessary is just to use the ion plating apparatus which provided the electron return electrode which surrounded the outer peripheral side of this insulating tube, and was made into the electric potential state higher than an exit part.

  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 occurrence of splash during film formation by the ion plating method can be suppressed, and the rapid change in electrical resistance of silicon nitride during plasma irradiation is suppressed. As a result, it is possible to provide a method for producing a gas barrier sheet capable of forming a gas barrier film that can suppress the occurrence of film defects, enable stable film formation, and can sufficiently enjoy the high gas barrier property of silicon nitride. Can do.

  In addition, the development of a device using a feedback electrode opened the way to successfully deposit silicon nitride, which is an insulating material, by ion plating. However, silicon nitride can still be used as an evaporation source for ion plating. It was difficult to use the material as it was. Therefore, in the present invention, a gas barrier film containing silicon nitride can be favorably ion-plated by using an evaporation source material obtained by adding an appropriate amount of a melt-type material to silicon nitride. Details of these points are the same as those already described in the explanation column of the raw material powder, the explanation column of the evaporation source material, and the explanation column of the manufacturing method of the evaporation source material, so that the explanation here is omitted to avoid repeated explanation. .

  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
A silicon nitride _Si 3 _{N 4} powder (Wako Pure Chemical Industries, Ltd., average particle diameter was measured with a particle size distribution meter, Coulter counter method: 0.5 [mu] m) with respect to 100 parts by weight, SiO ₂ powder is a silicon dioxide powder ( 30 parts by weight of Tosoh Silica, particle size distribution meter / coulter counter method measured average particle size: 2 μm) was added and mixed to obtain a raw material powder according to the present invention.

  This raw material powder is put into a 30 mm □ × 5 mm thick mold, pressed, and then placed in a firing furnace and kept in the atmosphere at 1000 ° C. for 1 hour. The evaporation source material for ion plating according to the present invention is obtained. Obtained. As a result of measuring the mass ratio of the obtained evaporation source material by an X-ray spectroscopic analyzer (XPS / ESCA) described later, 30 parts by weight of silicon dioxide is contained with respect to 100 parts by weight of silicon nitride, and the raw material powder It was consistent with the mixing ratio.

  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 using a dryer is used as a transparent film substrate. I set it.

Next, the produced evaporation source material was put into a crucible in a hollow cathode ion plating apparatus, 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 4 × 10 ⁻³ Pa and 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 evaporated while shining in a semi-molten state without causing an electrical malfunction of the apparatus during film formation. More specifically, it was confirmed that sublimation was performed by gradually reducing the size of each evaporation source material in a substantially rectangular parallelepiped while shining. And during the sublimation, no splash from the material was confirmed. Ion plating was performed for 5 seconds to deposit on the substrate to obtain a 40 nm thick SiON gas barrier film. 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 measured by ESCA (manufactured by VG Scientific, UK, model: LAB220i-XL), and the atomic ratio (atm%) of Si: O: N was 100: 107: 85. 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 software Eclipse version 2.1 attached to the above-mentioned ESCA apparatus, and uses peaks corresponding to binding energies of Si: 2p, N: 1s, C: 1s, and O: 1s. went. At this time, Shirley background is removed for each peak, and sensitivity coefficient correction of each element is performed on the peak area (N = 1.770, Si = 0.865, O = 2. 850) 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 O and N which are other components was calculated, and it was set as the component ratio.

When the water vapor transmission rate was measured as the gas barrier property, it was 5 × 10 ⁻² g / m ² / day. The water vapor transmission rate was measured at a temperature of 37.8 ° C. and a humidity of 100% RH using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON).

  The above experimental results are shown in Table-1.

(Example 2)
In Example 1, except that the content of silicon dioxide powder was 5 parts by weight, the evaporation source material had a mass ratio of silicon dioxide of 5 with respect to silicon nitride 100, and the film formation conditions were appropriately adjusted. Produced a gas barrier film in the same manner as in Example 1. Table 1 shows the size of the evaporation source material, the Si: O: N atomic ratio of the gas barrier film, and the water vapor transmission rate.

(Example 3)
In Example 1, except that the content of silicon dioxide powder was 50 parts by weight, the evaporation source material was 50% by mass of silicon dioxide with respect to silicon nitride 100, and the film formation conditions were appropriately adjusted. Produced a gas barrier film in the same manner as in Example 1. Table 1 shows the size of the evaporation source material, the Si: O: N atomic ratio of the gas barrier film, and the water vapor transmission rate.

Example 4
In Example 1, the content of the silicon dioxide powder was set to 30 parts by weight, the raw material powder was put into a 100 mm □ × 5 mmt mold, and the press working was performed. Thus, a gas barrier film was produced in the same manner as in Example 1 except that the mass ratio of silicon dioxide was 30 and the film formation conditions were adjusted appropriately. Table 1 shows the size of the evaporation source material, the Si: O: N atomic ratio of the gas barrier film, and the water vapor transmission rate.

(Comparative Example 1)
A gas barrier sheet was formed in the same manner as in Example 1 except that silicon dioxide, which is a melt-type material, was not used in Example 1 and the film formation conditions were appropriately adjusted. Splash was observed during film formation. In addition, when the light emission state of the plasma was confirmed when the film was formed, disorder was observed in the plasma irradiation, and the film could not be formed stably. Table 1 shows the size of the evaporation source material, the Si: O: N atomic ratio of the gas barrier film, and the water vapor transmission rate.

(Comparative Example 2)
In Example 1, the content of the silicon dioxide powder was 70 parts by weight, and in the evaporation source material, the mass ratio of silicon dioxide was 70 with respect to silicon nitride 100, and the film formation conditions were adjusted appropriately. Produced a gas barrier film in the same manner as in Example 1. No splash was observed during film formation. Table 1 shows the size of the evaporation source material, the Si: O: N atomic ratio of the gas barrier film, and the water vapor transmission rate.

It is a block diagram of a hollow cathode type ion plating apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Hollow cathode type ion plating apparatus 102 Vacuum chamber 103a Supply roll 103b Winding roll 104 Coating drum 105 Vacuum exhaust pump 106 Deposition chamber 107 Crucible 108 Anode magnet 109 Partition plate 110 Pressure gradient type plasma gun 111 Converging coil 112 Sheeting Magnet 113 Valve 114 Vacuum exhaust pump 116 Valve

Claims (8)

Silicon nitride having an average particle diameter of 5 μm or less and a molten material that is silicon oxide or silicon oxynitride having an average particle diameter of 5 μm or less, and the content of the molten material is 100 parts by weight of the silicon nitride On the other hand, the raw material powder of the evaporation source material for ion plating, which is 5 parts by weight or more and 50 parts by weight or less. Used as a raw material powder of the evaporation source material for pressure gradient type ion plating, the raw material powder for ion plating evaporation source material according to claim 1. An ion plating method comprising: preparing a raw material powder of the evaporation source material for ion plating according to claim 1; and sintering the raw material powder to process the raw material powder into a predetermined shape. Of manufacturing evaporation source material. The method for producing an evaporation source material for ion plating according to claim 3 , wherein the step of processing into the predetermined shape is a step of sintering the raw material powder to process into a substantially rectangular parallelepiped shape having a side of 5 mm or more. Silicon nitride having an average particle diameter of 5 μm or less and a molten material that is silicon oxide or silicon oxynitride having an average particle diameter of 5 μm or less, and the content of the molten material is 100 parts by weight of the silicon nitride In contrast, an ion source evaporation source material obtained by sintering 5 parts by weight or more and 50 parts by weight or less of raw material powder,
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 5 , which is used as an evaporation source material for pressure gradient ion plating. The evaporation source material for ion plating according to claim 5 or 6 , wherein one side has a substantially rectangular parallelepiped shape with 5 mm or more. A step of preparing the ion plating evaporation source material according to any one of claims 5 to 7 , and using the ion plating evaporation source material as an evaporation source material to form a gas barrier film on the substrate. A gas barrier sheet manufacturing method comprising the steps of:

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