JP4877510B2 - Raw material powder for ion plating evaporation source material, evaporation source material for ion plating, method for producing the same, and method for producing gas barrier sheet - Google Patents

Description

  The present invention relates to a raw material powder of an evaporation source material for ion plating suitable for the 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 or the like of an evaporation source material for ion plating that can form a high, dense, and highly adherent gas barrier film.

  As a gas barrier sheet having a barrier property against oxygen gas, water vapor or 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.

Regarding a gas barrier film having such characteristics and a manufacturing method thereof by ion plating, for example, Patent Document 1 discloses that silicon having a sintering density of 80% or more and SiOx having a sintering density of 80% or more (x is The atomic ratio is in the range of Si: O: C = 100: 160 to 190: 30-50 by ion plating in the presence of oxygen gas using any one of 1-2) as a film forming material, and Si—O Based on a silicon oxide film in which infrared absorption by Si stretching vibration exists in the range of 1030 to 1060 cm ⁻¹ , the film density is in the range of 2.5 to 2.7 g / cm ³ , and the inter-grain distance is 30 nm or less. A method for producing a barrier film characterized by forming a barrier layer on a material has been proposed. For example, Patent Document 2 proposes a gas barrier sheet characterized in that a multi-element inorganic oxide thin film containing at least silicon oxide and aluminum oxide is formed on the surface of a plastic film.
JP 2003-305801 A JP 2000-334878 A

  The gas barrier sheet proposed in Patent Documents 1 and 2 and the manufacturing method thereof are preferable to the vacuum deposition method and the sputtering method in consideration of both the productivity and the film characteristics. Yes. In recent years, research and development has been carried out to further increase the productivity of gas barrier sheets formed by forming a gas barrier film by an ion plating method.

  An object of the present invention is to provide a raw material powder or the like of an evaporation source material for ion plating capable of forming a gas barrier film having high productivity and high density, and is suitable for the ion plating method in detail. It is another object of the present invention to provide a raw material powder for an ion plating evaporation source material, an ion plating evaporation source material and a manufacturing method thereof, a gas barrier sheet and a manufacturing method thereof.

  The present inventor improved the evaporation source material used in the ion plating method in the course of conducting research and development to further increase the productivity of the gas barrier sheet, and as a result, the evaporation rate was remarkably increased. It has been found that the film formation rate is increased, the productivity is remarkably improved, and the film characteristics are also improved.

  The raw material powder of the evaporation source material for ion plating according to the present invention for solving the above-mentioned problems is composed of silicon dioxide powder having an average particle size of 5 μm or less, silicon carbide powder and / or silicon monoxide having an average particle size of 5 μm or less. And a silicon compound powder made of powder.

  According to the present invention, if an evaporation source material obtained by sintering or granulating the raw material powder is used as an evaporation source for ion plating, evaporation of the evaporation source is facilitated and ionization is facilitated. As a result, the film formation rate (deposition rate) on the substrate is increased, the productivity of the gas barrier sheet can be improved, and a dense and highly adherent gas barrier film can be obtained. The reason why the evaporation source material obtained by sintering or granulating the raw material powder of this invention has the above-mentioned effect is that by mixing a silicon compound powder having an average particle size of 5 μm or less with a silicon compound powder having an average particle size of 5 μm or less, During sintering or granulation, it does not cause a phase change in the order of solid phase → liquid phase → gas phase, but causes a sublimation phenomenon of solid phase → gas phase, and evaporation due to such sublimation phenomenon. The phase change of the source material enables evaporation with a small amount of energy, and facilitates ionization of the evaporated atoms, thereby increasing the ionization rate and increasing the film formation rate (deposition rate).

In the raw material powder of the evaporation source material for ion plating of the present invention, it is preferable that the silicon dioxide powder has a specific surface area of 600 m ² / g or more.

According to the present invention, since the specific surface area of the silicon dioxide powder is 600 m ² / g or more, the silicon compound powder to be mixed is easily adsorbed, and a good Si—C network can be incorporated in the Si—O network.

  The raw material powder of the evaporation source material for ion plating of the present invention is configured such that the silicon compound powder is added in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the silicon dioxide powder. Is preferred.

  According to the present invention, since the silicon compound powder is added in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the silicon dioxide powder, the sublimation phenomenon can be facilitated while maintaining the characteristics of the gas barrier film. Therefore, a gas barrier film with good film quality can be efficiently formed.

  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 comprises 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. Alternatively, the sintered ion-plating evaporation source material having a predetermined shape does not cause a phase change in the order of solid phase → liquid phase → gas phase, but causes a solid phase → gas phase sublimation phenomenon. Such an evaporation source material can be evaporated with a small amount of energy, and ionization of evaporated atoms is facilitated, so that the ionization rate is increased and the film formation rate (deposition rate) can be increased. As a result, the produced evaporation source material for ion plating is extremely effective as an evaporation source material that enables the formation of a dense and highly adherent gas barrier film.

  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 performed by sintering or granulating the silicon dioxide powder and the silicon compound powder constituting the raw material powder. It is preferably a process of processing into a lump particle or lump of 2 mm or more.

  According to the present invention, in the step of processing into a predetermined shape, the silicon dioxide powder and the silicon compound powder constituting the raw material powder are sintered or granulated to be processed into block particles or blocks having an average particle diameter of 2 mm or more. Therefore, scattering during evaporation of the evaporation source can be prevented.

  An evaporation source material for ion plating according to the present invention for solving the above-mentioned problems is an average particle sintered or granulated with silicon dioxide powder and silicon compound powder comprising silicon carbide powder and / or silicon monoxide powder. An evaporation source material for ion plating composed of massive particles or aggregates having a diameter of 2 mm or more, and when the evaporation source material for ion plating is heated, vaporization of the evaporation source material does not go through a liquid phase It is characterized by occurring.

  According to this invention, when an evaporation source material for ion plating composed of lump particles or lump having an average particle diameter of 2 mm or more sintered or granulated with silicon dioxide powder and silicon compound powder is heated, Since vaporization of the source occurs without going through the liquid phase, evaporation with little energy is possible and ionization of the evaporated atoms is facilitated. As a result, the ionization rate increases and the film formation rate (deposition rate) can be increased. In addition, conventional evaporation source materials for ion plating have been studied by vapor deposition material manufacturers, but many of them use vacuum evaporation source materials and sputtering target materials as they are, improving the deposition rate. In fact, no evaporation source material for ion plating has been proposed for the purpose of improving film quality.

  In the evaporation source material for ion plating of the present invention, it is preferable that the mass ratio of the silicon compound is 10 to 50 when the silicon dioxide is 100.

  According to this invention, since the mass ratio of the silicon compound is contained in the above range, the sublimation phenomenon can be facilitated while maintaining the characteristics of the gas barrier film. As a result, a gas barrier film with good film quality can be efficiently formed.

  A method for producing a gas barrier sheet of the present invention that solves the above-mentioned problems is a silicon compound powder comprising a silicon dioxide powder having an average particle size of 5 μm or less, a silicon carbide powder having an average particle size of 5 μm or less, and / or a silicon monoxide powder. A step of preparing a predetermined shape of the evaporation source material for ion plating obtained by granulating or sintering a raw material powder of the evaporation source material for ion plating, and the evaporation source material for ion plating as an evaporation source material And a step of forming a gas barrier film on the substrate by ion plating.

  According to this invention, the step of preparing the above-described 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 raw material. In particular, by using the evaporation source material for ion plating according to the present invention, the evaporation source material can evaporate with a little energy by causing a solid phase → gas phase sublimation phenomenon. Facilitates ionization of evaporated atoms. As a result, the ionization rate can be increased to increase the deposition rate (deposition rate), and a dense gas barrier film with good adhesion can be formed.

  The gas barrier sheet of the present invention for solving the above problems is a gas barrier sheet comprising a gas barrier film on at least one surface of a substrate, wherein the gas barrier film does not contain an alkyl group or an alkylene group as a carbon source. And an Si—O—C film having a Si: O: C atomic ratio of 100: 150 to 180: 20 to 140, wherein the atomic ratio is uniform in the thickness direction of the gas barrier film. It is characterized by being.

  According to the present invention, the gas barrier film does not contain an alkyl group or an alkylene group as a carbon source, and the Si—O— is in the range of 100: 150 to 180: 20 to 140 in terms of the number ratio of Si: O: C. Since it is a C film and the atomic ratio is uniform in the thickness direction of the gas barrier film (variation is within ± 10%), a gas barrier sheet having a gas barrier film with a uniform film quality in the thickness direction can be provided. . Note that the atomic ratio shown in the present application indicates a value in bulk.

  According to the raw material powder of the evaporation source material for ion plating of the present invention, this raw material powder is sintered or granulated and used as an evaporation source for ion plating, thereby facilitating evaporation of the evaporation source and ionization. Can be made easier. As a result, the film formation rate (deposition rate) on the substrate is increased, the productivity of the gas barrier sheet can be improved, and a dense and highly adherent gas barrier film can be obtained.

  According to the method for producing an ion plating evaporation source material of the present invention, the granulated or sintered ion plating evaporation source material having a predetermined shape is subjected to a phase change in the order of solid phase → liquid phase → gas phase. Therefore, the evaporation source material can be evaporated with a small amount of energy and ionization of evaporated atoms is facilitated. As a result, the produced ion source evaporation source material can increase the ionization rate and increase the deposition rate (deposition rate), and enables the formation of a dense and highly adherent gas barrier film. It is extremely effective as an evaporation source material.

  According to the evaporation source material for ion plating of the present invention, evaporation with a small amount of energy is possible and ionization of evaporated atoms is facilitated, so that the ionization rate is increased and the film formation rate (deposition rate) is increased. Can be increased. 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 no evaporation source material for ion plating has been proposed for the purpose of improving the film formation rate and film quality.

  According to the method for producing a gas barrier sheet of the present invention, particularly by using the evaporation source material for ion plating of the present invention, the evaporation source material causes a solid phase → gas phase sublimation phenomenon with little energy. Vaporization of the vaporized atoms becomes possible, and ionization of the vaporized atoms is facilitated. As a result, the ionization rate can be increased to increase the deposition rate (deposition rate), and a dense gas barrier film with good adhesion can be formed.

  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 a good adhesiveness is provided, a gas barrier sheet having excellent gas barrier properties can be provided.

  Hereinafter, the raw material powder of the ion plating evaporation source material suitable for the ion plating method of the present invention, the ion plating evaporation source material and the manufacturing method thereof, the gas barrier sheet and the manufacturing method thereof will be described in order.

(Raw material powder of evaporation source material for ion plating)
A raw material powder of an evaporation source material for ion plating according to the present invention (hereinafter referred to as “raw material powder”) is a raw material of an evaporation source material used as an evaporation source of atoms to be ionized in an ion plating method. Is a raw material powder having a silicon dioxide powder having an average particle size of 5 μm or less and a silicon compound powder comprising a silicon carbide powder and / or a silicon monoxide powder having an average particle size of 5 μm or less.

The silicon dioxide powder constituting the present invention has an average particle diameter of 5 μm, which can be represented by SiO _x (where x is in the range of 1.8 to 2.2 and is usually represented by SiO ₂ ). The following powder. In the present application, the “average particle diameter” is a result obtained by measuring a predetermined amount (for example, 1 g) of powder with a particle size distribution meter (Coulter counter method).

  The silicon compound powder constituting the present invention is a powder composed of a silicon carbide powder and / or a silicon monoxide powder, and each is 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. Note that the silicon carbide powder and the silicon monoxide powder may be used alone or in combination.

The silicon carbide powder can be represented by SiC _x (where x is in the range of 0.8 to 1.2 and is usually represented by SiC), and is very suitable as the raw material powder of the present invention. Yes. The reason is based on various characteristics of SiC. Examples of the characteristics include affinity with SiO ₂ , heat resistance, conductivity, and plasma resistance.

The silicon monoxide powder can be represented by SiO _x (where x is in the range of 0.9 to 1.1 and is usually represented by SiO), and is suitable as the raw material powder of the present invention. . The reason is based on various characteristics of SiO. Examples of the characteristics include affinity with SiO ₂ , heat resistance, conductivity, plasma resistance, and the like.

  In the raw material powder of the present invention, the average particle diameter of the silicon dioxide powder and the average particle diameter of the silicon compound powder are both 5 μm or less, preferably 3 μm or less. If powder materials within this range are used, mixing of the powder materials is easy, and a raw material powder having no dispersion unevenness can be obtained. If the raw material powder is sintered or granulated to produce an evaporation source material for ion plating, a fine silicon dioxide powder in a small area per unit volume and a silicon compound powder of a different type from the silicon dioxide powder. It exists uniformly, and individual powders can be easily exposed to the plasma generated in the ion plating apparatus. In particular, in the present invention, since the silicon compound powder exists so as to be uniformly mixed in the silicon dioxide powder, the mixed powder becomes a phase in the order of solid phase → liquid phase → gas phase by the action of the silicon compound powder. It does not cause a change and causes a solid phase → gas phase sublimation phenomenon. This phase change of the evaporation source material due to the sublimation phenomenon makes it possible to evaporate with a small amount of energy, and also facilitates ionization of the evaporated atoms, increasing the ionization rate and increasing the film formation rate (deposition rate). Become.

  The lower limit of the average particle size is not particularly limited, but is preferably 0.2 μm. When the average particle size is less than 0.2 μm, there is a problem that the powder materials are likely to be scattered when the powder materials are mixed or during sintering / granulation.

  On the other hand, when one or both of the two powders exceed the average particle size of 5 μm, dispersion does not occur sufficiently even when 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 dioxide powder and silicon dioxide powder in a small area per unit volume Since different types of silicon compound powder do not exist uniformly, the action of the silicon compound powder causing the sublimation phenomenon described above is difficult to occur, and as the average particle size becomes larger, the phase change from solid phase to gas phase A phase change of solid phase → liquid phase → gas phase is likely to occur. The phase change of the evaporation source material has a larger energy for evaporation than the average particle size of 5 μm or less, so when the same energy is given, the evaporation amount decreases, and the film formation rate (deposition rate) Becomes smaller.

The specific surface area of the silicon dioxide powder is preferably 600 m ² / g or more. By setting the specific surface area of the silicon dioxide powder to 600 m ² / g or more, it is easy to adsorb the silicon compound powder to be mixed, and a good Si—C network can be incorporated into the Si—O network. For example, even if the powder has the same volume, if a powder having a specific surface area of 600 m ² / g or more is used, the functional groups (silanol groups) of the primary particles are increased and there are many adsorption sites. When the specific surface area of the silicon dioxide powder is less than 600 m ² / g, the adsorptivity to SiC, SiO and the like is insufficient, and a good Si—C network may not be incorporated in the Si—O network. Moreover, if the specific surface area of a silicon dioxide powder is less than 600 m < ² > / g, even if it sinters or granulates, it is hard to solidify and it cannot be made into a desired lump particle or lump. In the present application, the specific surface area was evaluated by a value obtained by determining a predetermined amount (for example, 1 g) of powder with an automatic specific surface area measuring apparatus (nitrogen adsorption method, BET formula).

At this time, the evaluation of whether the Si-C network was successfully incorporated into the Si-O network was performed by measuring the film quality of the gas barrier film obtained by the ion plating method, and C was uniformly distributed in the gas barrier film. And that the gas barrier film is dense. In addition, the preferable specific surface area of a silicon dioxide powder is 800 m < ² > / g or more, Although the upper limit is not specifically limited, The thing about 1000 m < ² > / g can be used. In addition, when silicon monoxide (SiO) is used as the silicon compound powder, the constituent elements are the same as the silicon dioxide powder, but cannot be distinguished from each other. However, when evaluated from the characteristics of the obtained gas barrier film, it is the same as in the case of SiC. is there.

  As the addition amount of the silicon compound powder in the mixed powder, it is preferable that the silicon compound powder is added in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the silicon dioxide powder. Evaporation and ionization by the above-mentioned sublimation phenomenon can be easily performed by producing an evaporation source material for ion plating with a mixed powder containing silicon compound powder within this range, and performing ion plating using the evaporation source material. In addition, it is possible to obtain a dense gas barrier film having good adhesion. The amount added at this time applies to both silicon carbide and silicon monoxide.

  When the silicon compound powder is less than 10 parts by weight with respect to 100 parts by weight of the silicon dioxide powder, the addition effect of the silicon dioxide powder (that is, the effect of sublimation) may not occur, and when it exceeds 50 parts by weight, Since the obtained gas barrier film is often colored brown, for example, when the gas barrier film is formed on a transparent member, the upper limit is set to 50 parts by weight from that viewpoint.

The purity of each powder used in the present invention is not particularly limited, but any of SiO ₂ , SiC, and SiO is preferably 99.9% or more.

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

In contrast to the evaporation source material of the present invention, when a readily available SiO ₂ material for vacuum deposition or the like is used as the evaporation source material for ion plating, the SiO ₂ material is vaporized after being once melted by heating. Therefore, thermal energy is used as the enthalpy of the phase change and is not energy efficient. As a result, there is a problem that electric energy loss due to plasma irradiation peculiar to the ion plating method occurs, and problems such as a decrease in film formation rate, a decrease in film adhesion, and a decrease in denseness are likely to occur. The same applies to the case where a readily available SiO ₂ target material for sputtering is used as the evaporation source material for ion plating. In any case, the raw material powder of the present invention that exhibits the above-described effects and the evaporation source material of the present invention obtained from the raw material powder have a significantly increased evaporation rate, and the film formation rate is increased, thereby significantly improving productivity. In addition, there is an effect that cannot be obtained by the conventional evaporation source material, that is, film characteristics are improved.

(Evaporation source material for ion plating)
The evaporation source material for ion plating of the present invention (hereinafter referred to as “evaporation source material”) is used as an evaporation source of atoms to be ionized in the ion plating method, and the raw material powder of the present invention is sintered. Or it is obtained by granulation. Specifically, an evaporation source composed of massive particles or massive substances having an average particle diameter of 2 mm or more sintered or granulated with silicon dioxide powder and silicon compound powder comprising silicon carbide powder and / or silicon monoxide powder The material is configured such that when the evaporation source material is heated, vaporization of the evaporation source material occurs without going through a liquid phase.

  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 average particle size is set to 2 mm or more. If the average particle size is less than 2 mm, the particles are fine and easily scattered due to the impact of plasma irradiation in the ion plating apparatus. Because of this. The upper limit of the average particle diameter is not particularly limited, but for example, it is about 5 mm, and the form may be a round shape, an oval shape, a square shape, 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 the silicon dioxide powder and the constituent elements of the silicon compound powder are uniformly distributed in the evaporation source material in the form of secondary particles. As a result, due to the action of the constituent elements of the silicon compound powder, The sublimation phenomenon can easily occur, and evaporation with a small amount of energy and ionization of the evaporated atoms can be facilitated.

  In the evaporation source material, the mass ratio of the silicon compound is preferably 10 or more and 50 or less when silicon dioxide is defined as 100. The reason for this is as described in the explanation section of the above mixed powder. If ion plating is performed using this evaporation source material, evaporation and ionization due to the sublimation phenomenon described above can be easily performed, A gas barrier film with good adhesion can be obtained. On the other hand, if the mass ratio of the silicon compound is less than 10 with respect to 100 of silicon dioxide, the sublimation phenomenon expression effect based on the action of silicon dioxide may not occur, and if it exceeds 50, the obtained gas barrier film may be, for example, Since it is often colored brown, when the gas barrier film is formed on the transparent member, the upper limit of the mass ratio of the silicon compound to the silicon dioxide 100 is set to 50 from that viewpoint.

  As described above, according to the evaporation source material for ion plating of the present invention, since evaporation occurs without passing through the liquid phase when heated in the ion plating apparatus, evaporation with a slight energy is possible. Facilitates ionization of evaporated atoms. As a result, the ionization rate increases and the film formation rate (deposition rate) can be increased. In addition, conventional evaporation source materials for ion plating have been studied by vapor deposition material manufacturers, but many of them use vacuum evaporation source materials and sputtering target materials as they are, improving the deposition rate. In fact, no evaporation source material for ion plating has been proposed for the purpose of improving film quality.

(Method of manufacturing evaporation source material for ion plating)
The method for producing an evaporation source material for ion plating according to the present invention (hereinafter referred to as “evaporation source material production method”) includes a step of preparing the raw material powder of the present invention, and granulating or sintering the raw material powder. And processing to a predetermined shape.

  The step of preparing the raw material powder includes the silicon dioxide powder having an average particle size of 5 μm or less, the silicon carbide powder and / or the silicon monoxide powder having an average particle size of 5 μm or less, as described in the explanation section of the raw material powder. A raw material powder having a silicon compound powder. The raw material powder to be prepared is, for example, a raw material powder in which silicon compound powder is added in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of silicon dioxide powder, for example, mixed by a mixing means such as a mixer. .

  The step of processing into a predetermined shape is a step of sintering or granulating the silicon dioxide powder and the silicon compound powder constituting the raw material powder to process them into massive particles or aggregates having an average particle diameter of 2 mm or more.

  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 desirably an arbitrary temperature of 500 ° C. or higher and 1500 ° C. or lower, and particularly preferably 750 ° C. or higher and 1200 ° 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 500 ° C., it may not be sufficiently sintered, and it may not be possible to obtain a massive particle or mass having an average particle diameter of 2 mm or more. If the sintering temperature exceeds 1500 ° C., SiC Is oxidized and its effect is lost.

  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 for obtaining massive particles having relatively high density by an operation of extruding a wet mass of raw material powder into a cylindrical shape from a small hole and drying it. Such a granulating means usually uses a binder. In this case, after the granulation, the binder is removed by heating and baking at an arbitrary temperature of, for example, 500 ° C. or higher and 1500 ° C. or lower. Even when the binder is not used, it is fired at an arbitrary temperature of, for example, 500 ° C. or more and 1500 ° C. or less. By these heating and baking, degassing can be sufficiently performed, and agglomerated particles or masses having an average particle diameter of 2 mm or more can be obtained.

  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 removed by heating and firing after sintering and granulation.

  As described above, according to the method for producing an evaporation source material of the present invention, it is possible to produce an evaporation source material that causes a sublimation phenomenon of solid phase → gas phase without causing a phase change in the order of solid phase → liquid phase → gas phase. By using such an evaporation source material, it is possible to evaporate with a small amount of energy, and it becomes easy to ionize the evaporated atoms, so that the ionization rate increases and the film formation rate (deposition rate) can be increased. . As a result, the produced evaporation source material for ion plating is extremely effective as an evaporation source material that enables the formation of a dense and highly adherent gas barrier film.

(Gas barrier sheet)
FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier sheet of the present invention. As shown in FIG. 1, the gas barrier sheet 1 of the present invention is provided with a gas barrier film 3 on at least one surface on a substrate 2, and the gas barrier film 3 is an alkyl group or alkylene group as a carbon source. And an Si—O—C film having a Si: O: C atomic ratio in the range of 100: 150 to 180: 20 to 140 (preferably 20 to 100). Is uniform in the thickness direction of the gas barrier film. Since the gas barrier sheet 1 has the gas barrier film 3 having a uniform film quality in the thickness direction, the gas barrier sheet 1 has excellent gas barrier properties.

The gas barrier film 3 mainly functions to block the permeation of gases such as oxygen and water vapor. The gas barrier film according to the present invention has an oxygen permeability of 1 cc / m ² / day · atm or less and a water vapor permeability of 1 or less. A high gas barrier property of 1 g / m ² / day or less is exhibited. The reason for exhibiting such a high gas barrier property is that the gas barrier film 3 is formed using the above-described ion plating evaporation source material of the present invention, and is higher than the case of using a conventionally known ion plating evaporation source material. This is because the film is formed at a film speed, is dense and dense, and has good adhesion.

  The thickness of the gas barrier film 3 is preferably 0.01 μm or more and 1 μm or less, particularly preferably 0.02 μm or more and 0.2 μm or less. When the thickness of the gas barrier film 3 is less than 0.01 μm, the above-described excellent oxygen permeability and water vapor permeability cannot be satisfied. In addition, when the thickness of the gas barrier film exceeds 1 μm, the film stress increases, and when the base material is a flexible film, the gas barrier film is liable to crack, the gas barrier property is lowered and the time required for film formation is increased. It is not preferable.

In the present application, “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, the evaporation source material of the present invention is obtained by sintering or granulating a raw material powder in which silicon dioxide powder (SiO ₂ ) and silicon compound powder (SiC, SiO) are mixed. When ion plating film formation is performed using a source material, the formed gas barrier film is substantially uniform in the thickness direction with the above-mentioned atomic ratio (the variation is within ± 10%, preferably within 5%). A film is formed. In addition, the atomic ratio shown in the present application indicates a value in a bulk, a natural oxide film may be formed on the film surface, and oxidation by a gas component from the base material may proceed at the interface with the base material. In any case, the composition may be 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 was performed using software Eclipse version 2.1 attached to the ESCA apparatus described above, and using peaks corresponding to the binding energies of Si: 2p, C: 1s, and O: 1s. At this time, Shirley background is removed for each peak, sensitivity coefficient correction for each element is performed on the peak area (Si = 0.817, O = 2.930 for C = 1), and atoms The number ratio was determined. About the obtained atomic ratio, the number of Si atoms was set to 100, the number of atoms of O and C which are other components was calculated, and it was set as the component ratio.

Moreover, the Si—O—C film as the obtained gas barrier film 3 has infrared absorption by Si—O—Si stretching vibration in a range of 1005 to 1060 cm ⁻¹ and a film density of 2.2 to 2.7 g. / Cm ³ , particularly preferably in the range of 2.5 to 2.7 g / cm ³ . If the atomic ratio of the gas barrier film, the infrared absorption band due to Si—O—Si stretching vibration, and the film density deviate from the above ranges, the denseness of the obtained gas barrier film is lowered, resulting in 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) or the film becomes hard and brittle, resulting in a decrease in durability. It is not preferable.

  In the present invention, the infrared absorption band due to Si—O—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. Measured using. Moreover, said film | membrane density was measured with the X-ray reflectivity measuring apparatus (The Rigaku Denki Co., Ltd. make, ATX-E). The gas barrier property can be measured with various measuring devices. The gas barrier property was 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 2 is preferably a material having a high degree of transparency. Specifically, the light transmittance at 400 nm to 700 nm is 70%. The above gas barrier sheet is required to see contents such as a display medium, illumination, a solar cell cover, etc., which needs to transmit light, or a package or a container. It can be preferably applied when used for applications. On the other hand, when the gas barrier sheet is used for an application that does not require transparency as described above, the gas barrier sheet may have a light transmittance of about 50%, and may be used as a general gas barrier sheet for other applications. Can be used. The light transmittance is used in the same meaning as the total light transmittance. However, since the 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 the gas barrier sheet of the present invention, the light transmittance also affects the atomic ratio of C in Si: O: C of the gas barrier film, and the atomic ratio of Si: O: C is 100: 150 to 180: 20 to In the case of 100, the light transmittance tends to be 70% or more, and it can be preferably used as a gas barrier sheet for the above-mentioned use (use requiring light transmission). On the other hand, when the atomic ratio of C in Si: O: C is more than 100 and less than or equal to 140, the light transmittance tends to be less than 70%, and other than the above uses (uses that require light transmission). It can be used as a general gas barrier sheet.

  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.

  The substrate 2 is a substrate to which the ion plating evaporation source material is attached, but 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 (PEN), polyamide, polyolefin, polyethylene naphthalate, polycarbonate, poly A flexible substrate such as acrylate, polymethacrylate, polyurethane acrylate, polyether sulfone, polyimide, polysilsesquioxane, polynorbornene, polyetherimide, polyarylate, and 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 form retainability, it is preferable to set it as the range of 6 micrometers or more and 400 micrometers or less, for example, preferably 12 micrometers or more and 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 about 5 nm to 500 μm.

  Such a resin layer may contain a non-fibrous inorganic filler having an average particle diameter in the range of 0.8 μm to 5 μm. 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 the range of 10 to 60% by weight, preferably 25 to 45% by weight of the resin layer.

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

(Method for producing gas barrier sheet)
The method for producing a gas barrier sheet of the present invention comprises an ion plate having a silicon dioxide powder having an average particle size of 5 μm or less and a silicon compound powder comprising a silicon carbide powder and / or a silicon monoxide powder having an average particle size of 5 μm or less. A step of preparing an ion plating evaporation source material having a predetermined shape obtained by granulating or sintering a raw material powder of a deposition evaporation source material, and the ion plating evaporation source material installed in an ion plating apparatus And ionizing atoms evaporated from the evaporation raw material to form a gas barrier film on the substrate.

  In this manufacturing method, each of the raw material powder, the evaporation source material, and the gas barrier sheet is as described above, and the description thereof is omitted here. Further, the method of sintering or granulating the raw material powder to make the evaporation source material is also as described in the explanation section of the above-described method of manufacturing the evaporation source material, and therefore 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, and a coating drum 104 disposed in the chamber 102. 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 chambers 102 and 106 are 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 chamber 106, which is between the vacuum exhaust pump 114 and the chamber 106. By controlling the degree of opening and closing of the valve, the inside of the chamber 106 is kept at a predetermined pressure, the base film is run, and power for plasma generation is applied to the pressure gradient plasma gun 110 into which argon gas is introduced at a predetermined flow rate, The crucible 107 on the anode magnet 108 is focused and irradiated to evaporate the film forming material, and the evaporated molecules are ionized by high density plasma to form the gas barrier film according to the present invention on the base film. Thus, a gas barrier sheet is obtained.

  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, vaporization from the evaporation source material causes a sublimation phenomenon that does not pass through the liquid phase, that is, a solid phase → gas phase sublimation phenomenon, and evaporation with a little energy occurs. It becomes possible, and ionization of the evaporated atom can be facilitated. As a result, the ionization rate can be increased to increase the deposition rate (deposition rate), and a dense gas barrier film with good adhesion can be formed.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

Example 1
SiO ₂ powder which is silicon dioxide powder (Made by Tosoh Silica, average particle size measured by particle size distribution meter / Coulter counter method: 2 μm, specific surface area measured by nitrogen adsorption method / BET formula with automatic specific surface area measuring device: 800 m ² / g) is mixed with 100 parts by weight of SiC, which is a silicon compound powder, 30 parts by weight of SiC (manufactured by High Purity Chemical Co., Ltd., average particle diameter measured by particle size distribution meter / Coulter counter method: 2 μm). The raw material powder according to the present invention was obtained. This raw material powder was put into a CIP device (hydrostatic pressure press device), held at a pressure of 2 t for 1 minute, and solidified to 50 mm □ (this □ is 50 mm × 50 mm). Then, it put into the baking furnace, hold | maintained at 1000 degreeC for 1 hour, and obtained the evaporation source material for ion plating which concerns on this invention which consists of a 50mm □ lump. 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 silicon carbide powder is 30 with respect to silicon dioxide 100, which is almost equal to the mixing ratio of the raw material powder. It was consistent.

  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 sublimated without showing a molten state (liquid phase state). Ion plating was performed for 5 seconds to deposit on the substrate to obtain a SiO _x C _y gas barrier film having a thickness of 108 nm. Note that sccm is an abbreviation for standard cubic centimeter per minute, and the same applies to the following examples and comparative examples.

The composition of the gas barrier film was measured by ESCA (manufactured by VG Scientific, UK, model: LAB220i-XL), and _x of SiO _x C _y was 1.6 and y was 0.4. 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 was performed using software Eclipse version 2.1 attached to the ESCA apparatus described above, and using peaks corresponding to the binding energies of Si: 2p, C: 1s, and O: 1s. At this time, Shirley background is removed for each peak, sensitivity coefficient correction for each element is performed on the peak area (Si = 0.817, O = 2.930 for C = 1), and atoms The number ratio was determined. About the obtained atomic ratio, the number of Si atoms was set to 100, the number of atoms of O and C which are other components was calculated, and it was set as the component ratio.

It was 2 * 10 < ^-1 > g / m < ² > / day when the water-vapor-permeation rate was measured as gas barrier property. The water vapor transmission rate was measured at a temperature of 37.8 ° C. and a humidity of 100% RH using a water vapor transmission rate measuring device (PERMATRAN-W 3/31 manufactured by MOCON). Moreover, it was 2 * 10 < ^-1 > cc / m < ² > / day * atm when oxygen permeability was measured. The oxygen gas permeability is measured by 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.

Moreover, about the obtained gas barrier film | membrane, the Fourier-transform type | mold infrared spectrophotometer (The JASCO Corporation make, Herschel FT-IR-) provided with the multiple reflection (ATR) measuring device for the infrared absorption by Si-O-Si stretching vibration. 610), it was confirmed that Si—O—Si stretching vibration was present in the vicinity of 1025 cm ⁻¹ . Moreover, when the film density of the obtained gas barrier film | membrane was measured with the X-ray reflectivity measuring apparatus (the Rigaku Denki Co., Ltd. make, ATX-E), it was confirmed that the film density is 2.5 g / cm < ³ >.

(Example 2)
The powder was rotated while dropping a 2% cellulose aqueous solution as a binder on the raw material powder according to the present invention produced in the same manner as in Example 1 to produce a spherical body of 5 mmφ. The spherical body was placed in a firing furnace, held at 1000 ° C. for 1 hour to remove the binder and sinter the raw material powder to obtain an evaporation source material for ion plating according to the present invention having a particle diameter of 5 mmφ. . 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 silicon carbide powder is 30 with respect to silicon dioxide 100, which is almost equal to the mixing ratio of the raw material powder. It was consistent.

Similarly to Example 1, a plastic film substrate made of 100 μm thick PEN resin (manufactured by Teijin DuPont, Q65) is used as a transparent film substrate, and the supply roll 103a of the pressure gradient ion plating apparatus having the structure shown in FIG. and set between the take-up roll 103b, then, by performing the same ion plating film forming operation as in example 1 to obtain a gas barrier film of _SiO x _{C y} film thickness 110 nm.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 1.8 and y was 0.4. The measured water vapor permeability in the same manner as in Example 1, was ^{3 × 10 -1 g / m 2} / day, was measured for oxygen ^{permeability, 1.5 × 10 -1 cc / m} 2 / Day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1022 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.6 g / cm ³ .

(Example 3)
An evaporation source material for ion plating was obtained in the same manner as in Example 1 except that SiO ₂ powder (manufactured by Tosoh Silica) having an average particle size of 5 μm measured by a particle size distribution meter / Coulter counter method was used. to obtain a gas barrier film of _SiO x _{C y} film thickness 110nm in the same manner as example 1.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 1.6 and y was 0.3. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 2.0 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, 2.0 × 10 ⁻¹ cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1028 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.4 g / cm ³ .

Example 4
For ion plating in the same manner as in Example 1 except that SiO ₂ powder (manufactured by Tosoh Silica) having a specific surface area of 600 m ² / g measured by the nitrogen adsorption method / BET equation with an automatic specific surface area measuring device was used. An evaporation source material was obtained, and a SiO _x C _y gas barrier film having a thickness of 75 nm was obtained in the same manner as in Example 1.

According to the same ESCA measurement as that of Example 1, _x of SiO _x C _y was 1.7 and y was 0.3. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 7.5 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, 9.5 × 10 ⁻¹ cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1045 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.2 g / cm ³ .

(Example 5)
Except for adding 10 parts by weight of SiC used in Example 1 to 100 parts by weight of SiO ₂ powder used in Example 1 and mixing, an evaporation source material for ion plating was obtained in the same manner as in Example 1, Further, a SiO _x C _y gas barrier film having a film thickness of 75 nm was obtained in the same manner as in Example 1.

According to the ESCA measurement similar to that of Example 1, _x of SiO _x C _y was 1.8 and y was 0.2. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 4.0 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, 4.0 × 10 ⁻¹ cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1040 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.3 g / cm ³ .

(Example 6)
Except that 50 parts by weight of SiC used in Example 1 was added to and mixed with 100 parts by weight of SiO ₂ powder used in Example 1, an evaporation source material for ion plating was obtained in the same manner as in Example 1, Furthermore, a SiO _x C _y gas barrier film having a thickness of 105 nm was obtained in the same manner as in Example 1.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 1.7 and y was 1.0. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 2.5 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, 3.5 × 10 ⁻¹ cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1010 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.6 g / cm ³ .

(Example 7)
Evaporation source for ion plating in the same manner as in Example 1 except that 100 parts by weight of the SiO ₂ powder used in Example 1 was mixed with 30 parts by weight of SiO instead of SiC used in Example 1. The material was obtained, and a SiO _x gas barrier film having a film thickness of 95 nm was obtained in the same manner as in Example 1.

According to the ESCA measurement similar to that of Example 1, _x of SiO x was 1.5. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 3.0 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, 2.5 × 10 ⁻¹ cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1015 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.3 g / cm ³ .

(Example 8)
Granulation and sintering are performed in the same manner as in Example 1, and the obtained ion plating evaporation source material is sieved. Using the material having an average particle diameter of 2 mm, film thickness is obtained in the same manner as in Example 1. to obtain a gas barrier film of _SiO x _{C y} of 100 nm.

According to the ESCA measurement similar to that of Example 1, _x of SiO _x C _y was 1.6 and y was 0.4. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 2.6 × 10 ⁻¹ g / m ² / day, and when the oxygen transmission rate was measured, 3.1 × 10 ⁻¹ cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1025 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.5 g / cm ³ .

(Comparative Example 1)
100 parts by weight of the SiO ₂ powder used in Example 1 was used, but the SiC used in Example 1 was not mixed, and the others were obtained in the same manner as in Example 1 to obtain an evaporation source material for ion plating. A SiO _x C _y gas barrier film having a thickness of 105 nm was obtained in the same manner as in Example 1. Using this evaporation source material, the same ion plating film forming operation as in Example 1 was performed. At that time, it was confirmed that the evaporation source material in the crucible irradiated with plasma once became a molten state and vaporized through the molten state. When the vaporized has progressed, it opened the shutter, by adhering to 8 seconds substrate, to obtain a gas barrier film of _SiO x _{C y} film thickness 105 nm.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 2.6 and y was 0.1. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 1.5 g / m ² / day, and when the oxygen transmission rate was measured, it was 1.2 cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1050 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.0 g / cm ³ .

(Comparative Example 2)
An evaporation source material for ion plating was obtained in the same manner as in Example 1 except that 5 parts by weight of SiC used in Example 1 was added to and mixed with 100 parts by weight of SiO ₂ powder used in Example 1. . Using this evaporation source material, the same ion plating film forming operation as in Example 1 was performed. At that time, it was confirmed that the evaporation source material in the crucible irradiated with plasma once became a molten state and vaporized through the molten state. When the vaporized has progressed, it opened the shutter, by adhering to 7 seconds substrate, to obtain a gas barrier film of _SiO x _{C y} film thickness 110 nm.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 2.4 and y was 0.2. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 1.2 g / m ² / day, and when the oxygen transmission rate was measured, it was 1.0 cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1048 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.1 g / cm ³ .

(Comparative Example 3)
In Example 1, the temperature of the baking furnace was kept at 1600 ° C. for 1 hour to obtain an ion source evaporation source material. Other than that, the same ion plating film forming operation as in Example 1 was performed in the same manner as in Example 1, using the evaporation source material. At that time, it was confirmed that the evaporation source material in the crucible irradiated with plasma once became a molten state and vaporized through the molten state. When the vaporized has progressed, it opened the shutter, by adhering to 7 seconds substrate, to obtain a gas barrier film of SiO _x C _y film thickness 95 nm.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 2.5 and y was 0.1. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 1.4 g / m ² / day, and when the oxygen transmission rate was measured, it was 1.2 cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1050 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.0 g / cm ³ .

Wherein the composition ratio of the resulting vapor source material x2.5 in _SiO x _{C y,} a Y0.1, the composition ratio of the evaporation source material obtained in Example 1 (x1.6 in _SiO x _{C y,} However, the reason is that silicon carbide was oxidized and changed to silicon dioxide by setting the temperature of the firing furnace to 1600 ° C., and as a result, the composition ratio was more favorable. It was confirmed that a thick film could not be obtained. This result indicates that a temperature of the firing furnace (firing temperature) is preferably 1500 ° C. or less.

(Comparative Example 4)
SiO ₂ powder with a specific surface area of 280 m ² / g measured by the nitrogen adsorption method / BET equation with an automatic specific surface area measuring device (manufactured by Tosoh Silica, average particle diameter measured by a particle size distribution meter / Coulter counter method: 2 μm) Otherwise, the raw material powder was obtained in the same manner as in Example 1. Using this raw material powder, an evaporation source material was obtained in the same manner as in Example 1. However, even when pressure was applied with a CIP device, the material felt loose and did not harden.

(Comparative Example 5)
A raw material powder was obtained in the same manner as in Example 1 except that SiO ₂ powder (manufactured by Tosoh Silica) having an average particle diameter of 500 μm measured by a particle size distribution meter / Coulter counter method was used. It felt that it was mottled on SiO ₂ and was not mixed uniformly as a material.

(Comparative Example 6)
Granulation and sintering are performed in the same manner as in Example 1, and the obtained ion plating evaporation source material is sieved, and a film having an average particle size of less than 2 mm is used in the same manner as in Example 1. to obtain a gas barrier film of _SiO x _{C y} thickness 100 nm. On the surface of the obtained gas barrier film, point defects generated by the splash were generated.

According to the ESCA measurement similar to that of Example 1, _x of SiO _x C _y was 1.6 and y was 0.4. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 4.8 g / m ² / day, and when the oxygen transmission rate was measured, it was 6.3 cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1025 cm ⁻¹ . Further, when the film density of the obtained gas barrier film was measured, it was confirmed that the film density was 2.5 g / cm ³ .

(Comparative Example 7)
Except that 70 parts by weight of SiC used in Example 1 was added to and mixed with 100 parts by weight of the SiO ₂ powder used in Example 1, an evaporation source material for ion plating was obtained in the same manner as in Example 1, Further, a SiO _x C _y gas barrier film having a film thickness of 115 nm was obtained in the same manner as in Example 1.

According to the same ESCA measurement as in Example 1, _x of SiO _x C _y was 1.5 and y was 1.5. Further, when the water vapor transmission rate was measured in the same manner as in Example 1, it was 1.0 g / m ² / day, and when the oxygen transmission rate was measured, it was 8.0 cc / m ² / day · atm. It was confirmed that Si—O—Si stretching vibration of the obtained gas barrier film was present in the vicinity of 1002 cm ⁻¹ . The total light transmittance of the gas barrier sheet provided with the gas barrier film obtained in each of the above Examples and Comparative Examples was 70% or more, but all of the gas barrier sheet provided with this gas barrier film was used. The light transmittance was 65%.

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 (8)

And the average particle size is 5μm or less of silicon dioxide powder, an average particle diameter of less 5μm silicon carbide powder, the raw material powder for ion plating evaporation source material, characterized in Tona Rukoto. The raw material powder for the evaporation source material for ion plating according to claim 1, wherein the silicon dioxide powder has a specific surface area of 600 m ² / g or more. The raw material powder of the evaporation source material for ion plating according to claim 1 or 2, wherein the silicon carbide powder is added in an amount of 10 to 50 parts by weight with respect to 100 parts by weight of the silicon dioxide powder. Preparing a raw material powder of the evaporation source material for ion plating according to any one of claims 1 to 3,
And a step of granulating or sintering the raw material powder to process it into a predetermined shape. The step of processing into the predetermined shape is a step of sintering or granulating the silicon dioxide powder and the silicon carbide powder constituting the raw material powder to process into a lump particle or lump having an average particle size of 2 mm or more. The manufacturing method of the evaporation source material for ion plating of Claim 4. An evaporation source material for ion plating composed of massive particles or aggregates having an average particle diameter of 2 mm or more, sintered or granulated with silicon dioxide powder and silicon carbide 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 mass ratio of silicon carbide, when the silicon dioxide is 100, is 10 or more and 50 or less, for ion plating evaporation source material according to claim 6. And the average particle size is 5μm or less of silicon dioxide powder, an average particle diameter of less 5μm silicon carbide powder, having a predetermined shape raw material powders formed by granulation or sintering for ion plating evaporation source material Ru Tona ions Preparing an evaporation source material for plating; and
And a step of ion-plating a gas barrier film on a base material using the ion-plating evaporation source material as an evaporation raw material.

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