JP2009143759A - Raw material powder of evaporation source material for ion plating, evaporation source material for ion plating and its manufacturing method and gas barrier sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a raw material powder etc. of an evaporation source material for an ion plating having a high production stability and capable of forming a dense gas barrier film with a high gas barrier property, and specifically to provide the raw material powder of the evaporation source material for the ion plating suitable for an ion plating method, the raw material powder of the evaporation source material for the ion plating and its manufacturing method and a gas barrier sheet and its manufacturing method. <P>SOLUTION: The above problem is solved by the raw material powder containing ≥5 pts.wt. and ≤100 pts.wt. conductive material having an average particle size of ≤5 μm to 100 pts.wt. silicon nitride or silicon oxynitride having an average particle size of ≤5 μm. The conductive material is preferably at least one selected from among a metal oxide, a metal nitride and a metal oxynitride having conductivity. The evaporation source material for the ion plating is a product obtained by processing the raw material powder to a bulk particle or a bulk product by sintering or granulating the raw material powder having an average particle size of ≥2 mm. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a raw material powder of an evaporation source material for ion plating suitable for an ion plating method, an evaporation source material for ion plating and a manufacturing method thereof, a gas barrier sheet and a manufacturing method thereof. The present invention relates to a raw material powder of an evaporation source material for ion plating that can form a gas barrier film with good properties.

  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, silicon nitride has poor film stability when it is formed by vacuum ion plating, and when the state changes from solid to gas, the amount of current changes greatly, resulting in overcurrent. There is a problem that voltage drop occurs and 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. In addition, since the pixel pattern is etched with an acid or an alkali when used for a display application, there is a further problem that it is desired to further improve the corrosion resistance against such an acid or alkali.

  The present invention has been made in order to solve the above-mentioned problems. The primary purpose of the present invention is to evaporate for ion plating that can form a gas barrier film having high production stability, high density, and high gas barrier properties. 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.

  The present invention has been made to solve the above-mentioned problems, and a secondary purpose thereof is a raw material of an evaporation source material for ion plating capable of forming a gas barrier film having high heat resistance and corrosion resistance. Specifically, the present invention provides a raw material powder of an ion plating evaporation source material suitable for the ion plating method, an ion plating evaporation source material and a manufacturing method thereof, a gas barrier sheet and a manufacturing method thereof. It is to provide.

  In the course of research and development for improving gas barrier properties while improving productivity stability in a gas barrier sheet using silicon nitride or silicon oxynitride as a gas barrier film, the present inventor It has been found that by improving the evaporation source material used in the above, productivity is improved and gas barrier properties are remarkably improved. Furthermore, it has also been found that depending on the material combined with silicon nitride or silicon oxynitride, the corrosion resistance of the gas barrier film can be improved.

  The raw material powder of the evaporation source material for ion plating of the present invention for solving the above-mentioned problems is a conductive powder having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less. 5 to 100 parts by weight of a functional material is contained.

  According to this invention, ion plating containing 5 parts by weight or more and 100 parts by weight or less of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less. Since the raw material powder of the evaporation source material is used, when the evaporation source material obtained by sintering or granulating this raw material powder is used as the evaporation source for ion plating, the plasma irradiated during film formation is evaporated. The source material is intensively irradiated and easily penetrates into the evaporation source material through the conductive material, and the evaporation source material is efficiently excited. As a result, the gas barrier property of the gas barrier film to be formed is Is significantly improved.

  In the raw material powder of the evaporation source material for ion plating of the present invention, the conductive material is preferably at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity. .

  According to this invention, the conductive material is at least one selected from conductive metal oxides, conductive metal nitrides, and conductive metal oxynitrides. When the source material is obtained by sintering, the conductive material is difficult to oxidize during sintering, and tends to exist in silicon oxide while maintaining conductivity, and as a result, the composition of the evaporation source material can be easily controlled. Become.

  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 a vaporized or granulated evaporation source material is used as an evaporation source for ion plating, the plasma irradiated during film formation is concentrated on the evaporation source material and evaporated via the conductive material. It becomes easy to penetrate into the source material, and the evaporation source material is efficiently excited. As a result, the gas barrier property of the gas barrier film to be formed is remarkably improved.

  In the method of manufacturing an evaporation source material for ion plating according to the present invention, the step of processing into the predetermined shape includes sintering or granulating the silicon nitride or the silicon oxynitride and the conductive material constituting the raw material powder. It is preferable that the average particle size is a step of processing into a lump particle or lump having an average particle diameter of 2 mm or more.

  According to the present invention, the step of processing into a predetermined shape is performed by sintering or granulating silicon nitride or silicon oxynitride constituting the raw material powder and the conductive material, so that the average particle diameter is 2 mm or more. Therefore, it is easy to prevent scattering of the obtained evaporation source material during evaporation.

  The evaporation source material for ion plating of the present invention for solving the above-mentioned problems is obtained by using a conductive material having an average particle size of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle size of 5 μm or less. It is obtained by sintering or granulating a raw material powder of an evaporation source material for ion plating containing 5 parts by weight or more and 100 parts by weight or less, and is an aggregate particle or an aggregate having an average particle diameter of 2 mm or more .

  According to this invention, ion plating containing 5 parts by weight or more and 100 parts by weight or less of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less. Since it is used as an ion source evaporation source material that is obtained by sintering or granulating raw material powder for evaporation source material and having an average particle diameter of 2 mm or more, it is a plasma irradiated during film formation. However, the evaporation source material is intensively irradiated and easily penetrates into the evaporation source material through the conductive material, and the excitation of the evaporation source material is efficiently performed. As a result, a gas barrier film is formed. The gas barrier property is 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, it is preferable that the conductive material is at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity.

  According to this invention, the conductive material is at least one selected from conductive metal oxides, conductive metal nitrides, and conductive metal oxynitrides. When the source material is obtained by sintering, the conductive material is difficult to oxidize during sintering, and tends to exist in silicon oxide while maintaining conductivity, and as a result, the composition of the evaporation source material can be easily controlled. Become.

  The method for producing a gas barrier sheet of the present invention that solves the above-mentioned problems is obtained by adding 5 parts by weight of a conductive material having an average particle diameter of 5 μm or less to 100 parts by weight of silicon nitride or silicon oxynitride 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 a raw material powder of an ion plating evaporation source material containing 100 parts by weight or less; and the ion plating evaporation source material And a step of forming an ion plating film of a gas barrier film on a base material using as an evaporation source material.

  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 source evaporation source material of the present invention, the plasma irradiated at the time of film formation is intensively applied to the evaporation source material and the conductive material is used. Thus, the vapor source material can easily penetrate into the vapor source material, and the vapor source material is excited efficiently. As a result, the gas barrier property of the gas barrier film to be formed is significantly improved.

  In the method for producing a gas barrier sheet of the present invention, the conductive material is preferably at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity.

  According to this invention, the conductive material is at least one selected from conductive metal oxides, conductive metal nitrides, and conductive metal oxynitrides. When the source material is obtained by sintering, the conductive material is difficult to oxidize during sintering, and tends to exist in silicon oxide while maintaining conductivity, and as a result, the composition of the evaporation source material can be easily controlled. Become.

  The gas barrier sheet of the present invention for solving the above-mentioned problems is a gas barrier sheet comprising a gas barrier film on at least one surface of a substrate, wherein the gas barrier film is Si: N: X1 (where X1 is Zn or It is a Si—N—X1-O film having an atomic ratio of Sn): O in the range of 100: 50 to 120: 5 to 20:50 to 150.

  According to this invention, the gas barrier film is in the range of 100: 50 to 120: 5 to 20:50 to 150 in terms of the atomic ratio of Si: N: X1 (wherein X1 represents Zn or Sn): O. Since it is a certain Si—N—X1-O film, it becomes a gas barrier sheet having a gas barrier film having a uniform film quality in the thickness direction, and as a result, a gas barrier sheet that is remarkably excellent in gas barrier properties 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, when the evaporation source material obtained by sintering or granulating this raw material powder is used as the evaporation source for ion plating, irradiation is performed at the time of film formation. The plasma is focused on the evaporation source material and easily penetrates into the evaporation source material through the conductive material, so that the evaporation source material is excited efficiently, and as a result, a gas barrier is formed. The gas barrier property of the film is remarkably improved.

  According to the method for producing an ion source evaporation source material of the present invention, when a sintered or granulated evaporation source material is used as an ion plating evaporation source, plasma irradiated during film formation is evaporated. The source material is intensively irradiated and easily penetrates into the evaporation source material through the conductive material, and the evaporation source material is efficiently excited. As a result, the gas barrier property of the gas barrier film to be formed is Is significantly improved.

  According to the evaporation source material for ion plating of the present invention, plasma irradiated at the time of film formation is intensively applied to the evaporation source material and easily penetrates into the evaporation source material through the conductive material. The evaporation source material is excited efficiently, and as a result, the gas barrier property of the formed gas barrier film is remarkably 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, particularly by using the ion plating evaporation source material of the present invention, plasma irradiated at the time of film formation is intensively irradiated to the evaporation source material. Further, it easily penetrates into the evaporation source material through the conductive material, the excitation of the evaporation source material is efficiently performed, and as a result, the gas barrier property of the formed gas barrier film is remarkably improved.

  According to the gas barrier sheet of the present invention, the gas barrier sheet having a uniform film quality in the thickness direction, a high density, a denseness, and a good adhesion can be provided.

  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, 5 parts by weight or more and 100 parts by weight or less of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less contains.

  When an evaporation source material obtained from such a raw material powder is used as an evaporation source for ion plating, plasma irradiated at the time of film formation is intensively applied to the evaporation source material and through the conductive material. Penetration into the evaporation source material is facilitated, and excitation of the evaporation source material is efficiently performed. As a result, the gas barrier property of the formed gas barrier film is remarkably improved. The reason why the evaporation source material obtained by sintering or granulating the raw material powder has the above-described effects is presumed as follows.

  According to the study of the present inventors, 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, The electrical conductivity changes greatly with the change of state (solid phase → liquid phase (at least locally liquefied) → gas phase), so overcurrent, voltage drop, etc. occur and stable film formation occurs. I found it difficult. Therefore, in the present invention, by introducing a conductive material into the vapor deposition source material, there is an effect that the change in conductivity accompanying the phase change of silicon nitride or silicon oxynitride is reduced, and continuous film formation is good. Easier to do. This is because an evaporation source material is obtained by sintering or granulating a raw material powder of an ion source for ion plating obtained by adding a conductive material to silicon nitride or silicon oxynitride. By using it as an evaporation source, conductive material is introduced into the evaporation source material together with insulating materials such as silicon nitride and silicon oxynitride, so the plasma irradiated from the plasma gun is concentrated on the evaporation source material. It is presumed to be easier to be done.

  In other words, when plasma is irradiated to a single insulating material such as silicon nitride or silicon oxynitride, the plasma is discharged to a portion other than the charge-up on the surface of the material or the floating portion of the vapor deposition chamber (earth potential portion), and the plasma becomes unstable Therefore, it is difficult to perform continuous film formation. On the other hand, in the present invention, since the conductive material is introduced into the evaporation source material, there is an effect that plasma irradiation is easily concentrated on the evaporation source material, and it is easy to perform continuous film formation.

  Furthermore, in the present invention, since a predetermined amount of a conductive material having an average particle diameter of 5 μm or less is contained in silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less, a raw material powder having high dispersion uniformity is obtained. Also in the ion plating evaporation source material obtained from this raw material powder, it is presumed that the conductive material exists uniformly dispersed in silicon nitride or silicon oxynitride. Therefore, the conductive material uniformly dispersed in the evaporation source material has an effect that the plasma can easily penetrate into the evaporation source material.

  As described above, the action of the concentrated irradiation of the plasma to the evaporation source material and the action of the penetration of the plasma into the evaporation source material are synergistically performed to efficiently excite the evaporation source material. Guessed. Then, since the evaporation source material is excited efficiently, it is estimated that the ionization rate increases and the film quality of the gas barrier film is greatly 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 a conventionally known material can be used, which is suitable as the 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, 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.

  The conductive material is not particularly limited as long as it is a conductive material, and an inorganic material is preferably used. Examples of the conductive material include a material having a volume resistivity of 1.4 μΩ · cm or more and 1 kΩ · cm or less. In the present invention, the volume resistivity measured by the four-probe method according to JIS-K7194 is used. Examples of such conductive materials include metals, alloys, and conductive compounds.

  First, the case where a metal or an alloy is used as the conductive material will be described. When a metal or alloy is used as the conductive material, it is preferable to pay attention to the following matters depending on the material and the method for producing the evaporation source material. That is, the evaporation source material of the present invention can be obtained by granulating or sintering raw material powder and processing it into a predetermined shape as described later, but sintering using a metal or alloy as the conductive material. When the evaporation source material is formed by the above, it is desirable to control the degree of oxidation according to the type of metal or alloy. More specifically, metals and alloys have a tendency to be oxidized by reacting with oxygen in the atmosphere during sintering. For this reason, as the metal or alloy used for the raw material powder, it is preferable to use a material that can maintain conductivity even when slight oxidation occurs, or a material that can maintain conductivity even when oxidation progresses.

Examples of metals and alloys that can maintain conductivity even when slight oxidation occurs include, for example, aluminum, silicon, copper, silver, nickel, chromium, gold, platinum, indium, tin, zinc, gallium, germanium, and the metals of these metals. There may be mentioned at least one selected from alloys. Of these metals and alloys, aluminum will be described as an example. When aluminum is oxidized until it becomes Al ₂ O _3, it becomes insulating. However, the conductivity is maintained by controlling the amount of oxygen introduced to aluminum to be small. be able to. Therefore, when using a metal or alloy that can maintain conductivity even if slight oxidation occurs, the conductive material contained in the evaporation source material can be controlled by controlling various conditions such as temperature and atmosphere during sintering. Conductivity can be ensured. Among the above metals and alloys, preferred from the viewpoint of conductivity are gold, silver, copper, platinum, indium, tin, zinc, and alloys of these metals, and from the viewpoint of cost, preferably aluminum, tin, Zinc.

  Examples of metals and alloys that can maintain conductivity even when oxidation proceeds include indium, zinc, tin, cerium, and alloys of these metals. Taking zinc as an example of these metals and alloys, zinc has its own conductivity, but zinc oxide (ZnO), which is an oxide, also has conductivity, so the degree of oxidation is not particularly controlled. Also, the conductivity of the conductive material contained in the evaporation source material obtained by sintering can be ensured. Therefore, when such metals and alloys are used, it is not necessary to control the degree of oxidation of these materials. Of the above materials, preferred from the viewpoint of conductivity are indium, zinc, tin, and alloys of these metals, and preferred from the viewpoint of cost are zinc, an alloy of zinc, tin, and an alloy of tin. .

  On the other hand, when the raw material powder is granulated and processed into a predetermined shape to obtain the evaporation source material, it may not be necessary to consider the oxidation of the metal or alloy. For example, when the granulation is performed by a method such as pressing instead of sintering, the influence of the oxidation can be suppressed. Even when sintering is used, if the sintering is performed under an inert gas or under vacuum, the influence of the oxidation can be suppressed. For this reason, various materials can be used without considering a material that can maintain conductivity even when slight oxidation occurs, or a material that can maintain conductivity even when oxidation progresses. As such materials, specifically, the metals and alloys exemplified above may be used.

  Next, the case where a conductive compound is used as the conductive material will be described. Preferred examples of the conductive compound include at least one selected from conductive metal oxides, conductive metal nitrides, and conductive metal oxynitrides. Note that the metal oxides and metal nitrides include complex oxides and nitrides that are oxides and nitrides of two or more metal elements. The same applies to the metal element of the metal oxynitride. Since these conductive compounds are mostly oxidized and / or nitrided to be in a chemically stable state, they are hardly oxidized by sintering during the production of the evaporation source material, and silicon nitride is maintained while maintaining conductivity. Alternatively, since it is easily present in silicon oxynitride, the composition of the evaporation source material can be easily controlled. The conductive compound is preferably an oxide, nitride, or oxynitride of at least one element selected from indium, zinc, tin, and cerium from the viewpoint of the stability of conductivity, and more preferably, An oxide, nitride, or oxynitride of at least one element selected from indium, zinc, and tin is used. More preferably, an oxide, nitride, or oxynitride of at least one element selected from zinc and tin is used. Is used. More specifically, preferred examples of the conductive compound include zinc oxide, tin oxide, and ITO.

  In the present invention, it is preferable to use zinc oxide or tin oxide as the conductive material. These materials have good compatibility with silicon nitride or silicon oxynitride, and the effect of intensively irradiating the evaporation source material with plasma is easily exerted. The plasma penetrates into the evaporation source material through the conductive material. It becomes easy. As a result, the excitation of the evaporation source material is efficiently performed, and the effect of improving the gas barrier property of the gas barrier film to be formed is easily ensured. In addition, when tin oxide is used as the conductive material, the corrosion resistance of the gas barrier film is greatly improved. That is, when the gas barrier sheet is used for display, the pixel pattern is etched with acid or alkali. For this reason, it is necessary to further improve the corrosion resistance of the gas barrier film against acids and alkalis. Therefore, by using tin oxide as the conductive material, the corrosion resistance of the gas barrier film can be improved, and it becomes easy to provide a gas barrier sheet that can be used effectively for display applications.

  Among the conductive materials described above, when the evaporation source material is manufactured by sintering the raw material powder, it is not necessary to control the degree of progress of oxidation, and the composition of the resulting evaporation source material can be easily controlled for industrial production. From the viewpoint of being suitable for the metal, it is preferable to use a metal, an alloy, or a conductive compound that can maintain conductivity even when oxidation proceeds.

  The property of the conductive 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 conductive 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, the average particle diameter of silicon nitride or silicon oxynitride and the average particle diameter of the conductive material are both 5 μm or less, preferably 3 μm or less. If silicon nitride, silicon oxynitride, and a conductive material within this range are used, mixing of powder materials becomes easy, and a raw material powder with little dispersion unevenness can be obtained. If these source powders are sintered or granulated to produce an evaporation source material for ion plating, fine silicon nitride or silicon oxynitride and a fine conductive material are uniformly present in a small area per unit volume. Thus, each powder can be easily exposed to plasma generated in the ion plating apparatus. In particular, in the evaporation source material, there is a conductive material in silicon nitride or silicon oxynitride, so that the plasma irradiated from the plasma gun is concentrated on the evaporation source material by the action of the conductive material. The In addition, since the conductive material exists in silicon nitride and silicon oxynitride so as to be uniformly mixed, the plasma irradiated during film formation easily penetrates into the evaporation source material through the conductive material, The excitation of the evaporation source material is efficiently performed, and as a result, the gas barrier property of the gas barrier film to be formed is easily remarkably improved.

  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.

  On the other hand, when the average particle diameter of one or both of silicon nitride, silicon oxynitride, and the conductive material exceeds 5 μm, dispersion hardly occurs even if the powder materials are mixed. Therefore, even when the obtained raw material powder is sintered or granulated to produce an evaporation source material for ion plating, fine silicon nitride or silicon oxynitride in a small area per unit volume, and conductivity The material does not exist uniformly, and it becomes difficult to obtain the plasma intensive irradiation due to the presence of the above-mentioned conductive material and the penetration of the plasma into the evaporation source material through the conductive material. As the diameter increases, the excitation of the evaporation source material tends to become insufficient.

  The raw material powder for 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, and since silicon nitride is a material having a high refractive index, it can be suitably used as a raw material powder, an evaporation source material, and a gas barrier sheet. In the raw material powder of the evaporation source material for ion plating according to the present invention, plasma intensive irradiation due to the presence of the conductive material, and penetration of the plasma into the evaporation source material through the conductive material are performed. In order to improve the gas barrier property of the gas barrier film, a predetermined amount of conductive material is used. From such a viewpoint, the content of the conductive 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, based on 100 parts by weight of silicon nitride or silicon oxynitride. The amount is preferably 20 parts by weight or more, 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 is produced with a mixed powder containing a conductive material within this range, and ion plating is performed using the evaporation source material, the concentration of plasma due to the presence of the conductive material described above is achieved. Irradiation and plasma penetration into the evaporation source material through the conductive material are satisfactorily performed, the excitation of the evaporation source material is performed efficiently, and a gas barrier film having a high gas barrier property is easily obtained. In particular, when the content of the conductive material is 50 parts by weight or less, the gas barrier property of the gas barrier film can be dramatically improved.

  When the content of the conductive material is less than 5 parts by weight with respect to 100 parts by weight of silicon nitride or silicon oxynitride, the addition effect of the conductive material (that is, the intensive irradiation of the plasma and the plasma inside the evaporation source material is good) When the amount exceeds 100 parts by weight, the obtained gas barrier film is often colored brown or hard, for example, so that the gas barrier film is formed on a transparent member. When the flexibility of the gas barrier sheet is desired, the upper limit may be 100 parts by weight.

  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, the plasma irradiated during film formation is concentrated on the evaporation source material and easily penetrates into the evaporation source material through the conductive material. As a result, the gas barrier property of the formed gas barrier film is remarkably improved.

(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 the sintered or granulated evaporation source material is used as an evaporation source for ion plating, the plasma irradiated at the time of film formation is intensively applied to the evaporation source material and the conductive material. Thus, the evaporation source material can easily penetrate into the evaporation source material, and the evaporation source material is excited efficiently. As a result, the gas barrier property of the formed gas barrier film is remarkably improved.

  The step of preparing the raw material powder is, as described in the explanation section of the raw material powder, with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle size of 5 μm or less, conductivity having an average particle size of 5 μm or less. It is a step of preparing a raw material powder of an ion source evaporation source material containing 5 parts by weight or more and 100 parts by weight or less of a material. For the raw material powder to be prepared, for example, a raw material powder containing a conductive material in an amount of 5 parts by weight to 100 parts by weight with respect to 100 parts by weight of silicon nitride or silicon oxynitride is mixed by a mixing means such as a mixer. Is.

  The step of processing into a predetermined shape is not particularly limited, but the silicon nitride or silicon oxynitride constituting the raw material powder and the conductive material are sintered or granulated to form a lump or lump having an average particle size of 2 mm or more. It is preferable that it is the process processed into. 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. The effects of gas barrier properties and the like may disappear due to oxidation of the functional material and silicon nitride. For this reason, it is preferable to sinter in the atmosphere which interrupted oxygen so that an electroconductive material, 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 that case, after granulation, for example, the binder is generally removed by heating and baking at an arbitrary temperature of, for example, 200 ° C. or higher and 1500 ° C. or lower. . 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 evaporation source material manufacturing method of the present invention, the granulated or sintered ion source for ion plating having a predetermined shape is such that the plasma irradiated during film formation is concentrated on the evaporation source material. In addition to being irradiated, it easily penetrates into the evaporation source material through the conductive material, the excitation of the evaporation source material is efficiently performed, and as a result, the gas barrier property of the formed gas barrier film is remarkably improved.

(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. More specifically, for 100 parts by weight of silicon nitride or silicon oxynitride having an average particle size of 5 μm or less, for ion plating containing 5 to 100 parts by weight of a conductive material having an average particle size of 5 μm or less. It is obtained by sintering or granulating the raw material powder of the evaporation source material, and is configured to be massive particles or aggregates having an average particle diameter of 2 mm or more. As a result, the plasma irradiated at the time of film formation irradiates the evaporation source material intensively and easily penetrates into the evaporation source material through the conductive material, so that the evaporation source material is excited efficiently. As a result, the gas barrier property of the formed gas barrier film is remarkably improved. As the conductive material, it is preferable to use at least one selected from metal oxides, metal nitrides, and metal oxynitrides having conductivity. Since it is as described above, the description here is omitted to avoid duplication of explanation.

  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 constituent elements of silicon nitride or silicon oxynitride and the constituent elements of the conductive material are uniformly distributed in the evaporation source material in the form of secondary particles. As a result, the plasma is concentrated by the action of the constituent elements of the conductive material. The plasma easily penetrates into the inside of the evaporation source material through the conductive material, and the gas barrier film to be formed tends to be improved by the efficient excitation of the evaporation source material. Become.

  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, and since silicon nitride is a material having a high refractive index, it can be suitably used as a raw material powder, an evaporation source material, and a gas barrier sheet. In the ion plating evaporation source material of the present invention, the plasma barrier intensive irradiation due to the presence of the conductive material and the plasma penetration into the evaporation source material through the conductive material are achieved. A predetermined amount of conductive material is used to improve the gas barrier properties of the film. From such a viewpoint, the content of the conductive material in the ion plating evaporation source material is 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. Part by weight or more, more preferably 20 parts by weight or more, and 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 is produced with a mixed powder containing a conductive material within this range, and ion plating is performed using the evaporation source material, the concentration of plasma due to the presence of the conductive material described above is achieved. Irradiation and plasma penetration into the evaporation source material through the conductive material are satisfactorily performed, the excitation of the evaporation source material is performed efficiently, and a gas barrier film having a high gas barrier property is easily obtained. In particular, when the content of the conductive material is 50 parts by weight or less, the gas barrier property of the gas barrier film can be dramatically improved. In general, the content ratio of silicon nitride or silicon oxynitride in the evaporation source material for ion plating and the conductive material reflects the content ratio in the raw material powder.

  When the mass ratio of the conductive 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 often colored brown or hard, for example. . 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 conductive material to 100 parts by weight of silicon nitride or silicon oxynitride is 100 parts by weight. And it is sufficient.

  As described above, according to the evaporation source material for ion plating of the present invention, plasma is intensively irradiated from the plasma gun in the ion plating apparatus, and the plasma is radiated inside the evaporation source material through the conductive material. And the evaporation source material is efficiently excited. As a result, the gas barrier property of the gas barrier film to be formed is 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.

(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 includes a gas barrier film 3 on at least one surface on a base material 2, and the gas barrier film 3 includes silicon nitride or silicon oxynitride, It is formed from zinc oxide or tin oxide as a conductive material. Zinc oxide and tin oxide have good compatibility with silicon nitride or silicon oxynitride as explained in the explanation section of the raw material powder, and the effect of intensively irradiating the evaporation source material with plasma is easily exerted. It becomes easy to penetrate into the evaporation source material through the conductive material. As a result, the excitation of the evaporation source material is efficiently performed, and the effect of improving the gas barrier property of the gas barrier film to be formed is easily ensured. In addition, in tin oxide, the corrosion resistance of the gas barrier film is greatly improved, and can be effectively used for display applications having a step of patterning with acid or alkali.

  More specifically, the gas barrier film 3 has an atomic ratio of Si: N: X1 (where X1 is Zn or Sn): O in the range of 100: 50 to 120: 5 to 20:50 to 150. It is a Si-N-X1-O film. As a result, a gas barrier sheet having a gas barrier film having a uniform film quality in the thickness direction can be obtained, and as a result, a gas barrier sheet having significantly excellent gas barrier properties can be provided. X1 may be either Zn or Sn, but is preferably Sn from the viewpoint of corrosion resistance to acids and alkalis. The atomic ratio of N depends on the atomic ratio of other elements such as X1, but is preferably 55 or more, more preferably 60 or more, and preferably 118 or less, more preferably 115 or less. The atomic ratio of X1 is preferably 7 or more, more preferably 10 or more, and preferably 18 or less, more preferably 16 or less, from the viewpoint of ensuring gas barrier properties. The atomic ratio of oxygen depends on the atomic ratio of other elements such as X1, but is preferably 53 or more, more preferably 55 or more, and preferably 140 or less, more preferably 135 or less, even more preferably. Is 130 or less, particularly preferably 125 or less, and most preferably 120 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 software Eclipse version 2.1 attached to the above-mentioned ESCA apparatus, and binding of Si: 2p, N: 1s, Zn: 2p, Sn: 3d, O: 1s, C: 1s The peak corresponding to the energy was used. At this time, Shirley background is removed for each peak, and sensitivity coefficient correction of each element is performed on the peak area (Si = 0.865, N = 1.77, Zn = 18.0 for C = 1). 01, Sn = 14.63, 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 N, O, and X1 (Zn or Sn) which are other components was computed and made into 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 by using the above-described ion plating evaporation source material of the present invention, and the evaporation source is more than in the case of using a conventionally known ion plating evaporation source material. This is because excitation of the material is promoted, and it 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 (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.

(Method for producing gas barrier sheet)
In the method for producing a gas barrier sheet of the present invention, 5 parts by weight or more and 100 parts by weight or less of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less. A step of preparing a predetermined shape of the ion source evaporation source material obtained by sintering or granulating the raw material powder of the ion source evaporation source material contained therein, and using the ion plating evaporation source material as an evaporation source material And a step of forming a gas barrier film on the substrate by ion plating. In the method for producing a gas barrier sheet of the present invention, when the evaporation source material for ion plating of the present invention is used as an evaporation source for ion plating, the plasma irradiated during film formation is concentrated on the evaporation source material. , And easily penetrates into the evaporation source material through the conductive material, and the evaporation source material is efficiently excited. As a result, the gas barrier property of the formed gas barrier film is remarkably improved.

  In this manufacturing method, the raw material powder, the evaporation source material, and the gas barrier sheet are as described above. For example, the conductive material is preferably at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity as described above. 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 to form the vacuum exhaust pump 114. By controlling the degree of opening and closing of the valve between the membrane chamber 106, the inside of the chamber 106 is maintained at a predetermined pressure, the base film is run, and plasma is generated in the pressure gradient plasma gun 110 into which a predetermined flow rate of argon gas is introduced. Power is applied to the crucible 107 on the anode magnet 108 to converge and irradiate the plasma flow to evaporate the evaporation source material, ionize the evaporated molecules with high-density plasma, A gas barrier film is formed 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 plasma irradiated during film formation irradiates the evaporation source material intensively and penetrates into the evaporation source material through the conductive material. As a result, the evaporation source material is excited efficiently, and as a result, the gas barrier properties of the formed gas barrier film are remarkably improved.

  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
For 100 parts by weight of Si ₃ N ₄ powder (high purity chemical, average particle size: 1 μm), which is silicon nitride powder, zinc oxide (ZnO) powder (made by high purity chemical, particle size distribution meter / The average particle diameter measured by the Coulter counter method: 0.5 μm, 30 parts by weight of the volume resistivity measured by the four-probe method according to JIS-K7194 is added to 30 parts by weight, and the raw material according to the present invention is mixed. A powder was obtained.

  The raw material powder was rotated while dropping a 2% cellulose aqueous solution as a binder on the raw material powder to obtain a 10 mmφ spherical body. Then, it put into the baking furnace, hold | maintained at 400 degreeC for 1 hour, and obtained the evaporation source material for ion plating which concerns on this invention which consists of a lump with an average particle diameter of 7 mm (phi). As a result of measuring the mass ratio of the obtained evaporation source material with an X-ray spectroscopic analyzer (XPS / ESCA), the mass ratio of zinc oxide is 30 with respect to silicon dioxide 100, which is almost equal to the mixing ratio of the raw material powder. I did it.

  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 through a molten state. Ion plating was performed for 5 seconds (evaporation rate: 360 nm / min) to deposit on the substrate, thereby obtaining a SiNZnO gas barrier film having a thickness of 30 nm. Note that sccm is an abbreviation for standard cubic centimeter per minute, and the same applies to the following examples and comparative examples.

  When the composition of the gas barrier film was measured by ESCA (manufactured by VG Scientific, UK, model: LAB220i-XL), the Si: N: Zn: O atomic ratio was 100: 110: 15: 56 Si—N—Zn—. It was an O film. 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 binding of Si: 2p, N: 1s, Zn: 2p, Sn: 3d, O: 1s, C: 1s The peak corresponding to the energy was used. At this time, Shirley background is removed for each peak, and sensitivity coefficient correction of each element is performed on the peak area (Si = 0.865, N = 1.77, Zn = 18.0 for C = 1). 01, Sn = 14.63, O = 2.850), and the atomic ratio was determined. About the obtained atomic ratio, the number of Si atoms was set to 1 or 100, the number of atoms of N, O, and Zn which are other components was calculated, and it was set as the component ratio.

It was 1.4 * 10 ^<-2 > 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. These film forming conditions and evaluation results are shown in Table 1.

(Example 2)
SnO ₂ powder that is tin oxide instead of zinc oxide as a conductive material (manufactured by High Purity Chemical Co., Ltd., average particle diameter measured by a particle size distribution meter / Coulter counter method: 1.0 μm, 4-probe method according to JIS-K7194 And 10 parts by weight of SnO ₂ powder added to 100 parts by weight of Si ₃ N ₄ powder and mixing, and ion plating for 60 seconds ( A gas barrier sheet was formed in the same manner as in Example 1 except that the deposition rate was 21.7 nm / min) to obtain a SiNSnO gas barrier film having a thickness of 21.7 nm.

When ESCA was measured in the same manner as in Example 1, it was Si: N: Sn: O = 100: 63: 10: 133. Further, the water vapor transmission rate was measured to be 9.1 × 10 ⁻² g / m ² / day, and the oxygen transmission rate was measured to be below the measurement limit.

  Furthermore, when the total light transmittance of 400 nm-700 nm of a gas barrier sheet | seat was measured using the Suga Test Instruments haze meter, it was 88.1%. These film forming conditions and evaluation results are shown in Table 1.

(Corrosion resistance test)
The corrosion resistance test was conducted by the following method. That is, the gas barrier sheet was immersed in each of 1N-NaOH and 1N-HCl for 1 hour, rinsed with pure water, dried in an oven at 50 ° C./1 hour, and then visually checked for appearance and measured for water vapor permeability. Went. The above-mentioned method was used for the water vapor transmission rate measurement. As a result, no abnormality in appearance was observed in the gas barrier sheet, and the water vapor transmission rate was not changed.

(Example 3)
Example 2 except that 20 parts by weight of SnO ₂ powder was added to 100 parts by weight of Si ₃ N ₄ powder and mixed, and ion plating was performed for 30 seconds (deposition rate: 33.9 nm / min). Similarly, a gas barrier sheet was formed to obtain a SiNSnO gas barrier film having a thickness of 16.9 nm. When the water vapor transmission rate was measured, it was 3.9 × 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 87.7. %Met. These film forming conditions and evaluation results are shown in Table 1.

  Further, when the corrosion resistance test was conducted in the same manner as in Example 2, no abnormal appearance was observed in the gas barrier sheet, and the water vapor transmission rate was not changed.

Example 4
A gas barrier sheet was formed in the same manner as in Example 3 except that the ion plating was performed for 60 seconds (deposition rate: 56.1 nm / min) to obtain a SiNSnO gas barrier film having a film thickness of 56.1 nm. When ESCA was measured in the same manner as in Example 3, it was Si: N: Sn: O = 100: 97: 13: 69. Moreover, when the water vapor transmission rate was measured, it was 6.4 × 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 84. .2%. These film forming conditions and evaluation results are shown in Table 1.

  Further, when the corrosion resistance test was conducted in the same manner as in Example 2, no abnormal appearance was observed in the gas barrier sheet, and the water vapor transmission rate was not changed.

(Example 5)
Example 2 except that 30 parts by weight of SnO ₂ powder was added to 100 parts by weight of Si ₃ N ₄ powder and mixed, and ion plating was performed for 60 seconds (deposition rate: 38.1 nm / min). Similarly, a gas barrier sheet was formed to obtain a SiNSnO gas barrier film having a film thickness of 38.1 nm. When ESCA was measured in the same manner as in Example 2, it was Si: N: Sn: O = 100: 97: 15: 72. Moreover, when the water vapor transmission rate was measured, it was 4.8 × 10 ⁻² 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 85. 4%. These film forming conditions and evaluation results are shown in Table 1.

  Further, when the corrosion resistance test was conducted in the same manner as in Example 2, no abnormal appearance was observed in the gas barrier sheet, and the water vapor transmission rate was not changed.

(Example 6)
Example 2 except that 50 parts by weight of SnO ₂ powder was added to 100 parts by weight of Si ₃ N ₄ powder and mixed, and ion plating was performed for 60 seconds (deposition rate: 67.3 nm / min). In the same manner, a gas barrier sheet was formed to obtain a SiNSnO gas barrier film having a film thickness of 67.3 nm. When ESCA was measured in the same manner as in Example 2, it was Si: N: Sn: O = 100: 100: 15: 61. Further, the water vapor transmission rate was measured to be 7.1 × 10 ⁻² g / m ² / day, and the oxygen transmission rate was measured to be below the measurement limit. The total light transmittance of the gas barrier sheet was 80 0.7%. These film forming conditions and evaluation results are shown in Table 1.

  Further, when the corrosion resistance test was conducted in the same manner as in Example 2, no abnormality was observed in the appearance of the gas barrier sheet, and the water vapor transmission rate was not changed.

(Comparative Example 1)
An attempt was made to form a gas barrier sheet in the same manner as in Example 1 except that no ZnO 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. When the process was continued ignoring the warning, an SiNO gas barrier film having a film thickness of 24.2 nm was obtained by adhering to the substrate for 30 seconds. When ESCA was measured in the same manner as in Example 1, it was Si: N: O = 100: 88: 67. 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.

(Comparative Example 2)
Except that 3 parts by weight of ZnO powder was added to 100 parts by weight of Si ₃ N ₄ powder and mixed, and ion plating was performed for 30 seconds (deposition rate: 40.2 nm / min). Thus, a gas barrier sheet was formed to obtain a SiNZnO gas barrier film having a thickness of 20.1 nm. When ESCA was measured in the same manner as in Example 1, it was Si: N: Zn: O = 100: 44: 0.1: 130. Moreover, when the water vapor transmission rate was measured, it was 1.6 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, it was 2.7 × 10 ⁻¹ cc / m ² / day · atm. there were.

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 (9)

  For ion plating, comprising 5 to 100 parts by weight of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less Raw material powder of evaporation source material.   The raw material powder of the evaporation source material for ion plating according to claim 1, wherein the conductive material is at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity. Preparing a raw material powder of the evaporation source material for ion plating according to claim 1 or 2,
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 conductive material are sintered or granulated to form a lump particle or lump having an average particle diameter of 2 mm or more. The manufacturing method of the evaporation source material for ion plating of Claim 3 which is a process to process.   A raw material for an evaporation source material for ion plating containing 5 to 100 parts by weight of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less An evaporation source material for ion plating, which is obtained by sintering or granulating powder, and is an aggregate particle or an aggregate having an average particle diameter of 2 mm or more.   The evaporation source material for ion plating according to claim 5, wherein the conductive material is at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity. A raw material for an evaporation source material for ion plating containing 5 to 100 parts by weight of a conductive material having an average particle diameter of 5 μm or less with respect to 100 parts by weight of silicon nitride or silicon oxynitride having an average particle diameter of 5 μm or less Preparing an evaporation source material for ion plating having a predetermined shape obtained by sintering or granulating powder;
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 7, wherein the conductive material is at least one selected from metal oxide, metal nitride, and metal oxynitride having conductivity. In a gas barrier sheet comprising a gas barrier film on at least one surface on a substrate,
Si—N— in which the gas barrier film is in the range of 100: 50 to 120: 5 to 20:50 to 150 in terms of the atomic ratio of Si: N: X1 (wherein X1 represents Zn or Sn): O. A gas barrier sheet, which is an X1-O film.

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