JP2014058727A - Material for vapor deposition, and transparent gas barrier vapor deposition film - Google Patents

Abstract

An object of the present invention is to provide a vapor deposition material containing silicon and silicon oxide capable of suppressing the occurrence of a splash phenomenon, and a transparent gas barrier vapor deposition film formed by heating vapor deposition using the material.
A heating type vapor deposition material in which metallic silicon and silicon oxide are mixed, wherein the bulk density is in a range of 0.6 g / cm ³ or more and less than 2.0 g / cm ³ . ,
The ratio of the number of oxygen atoms to silicon (O / Si) is in the range of 1.2 to 2.0, and the silicon oxide is silicon dioxide containing at least 20% of crystal structure. It is a material for vapor deposition.
[Selection] Figure 1

Description

  The present invention relates to a vapor deposition material and a transparent gas barrier vapor deposition film.

  The transparent gas barrier vapor-deposited film is widely used in the field of materials that need to barrier oxygen and water vapor in the field of packaging for solar cells, such as back sheets and front sheets, foods and pharmaceuticals, or non-packaging fields.

  Packaging materials used for packaging precision electronic components such as foods, pharmaceuticals, hard disks and semiconductor modules must protect the contents. In particular, in food packaging, it is used to suppress oxidation and alteration of proteins, fats and oils, and to maintain taste and freshness.

  In addition, for pharmaceuticals that require handling under aseptic conditions, the alteration of the active ingredient is suppressed and its efficacy is maintained. In addition, in precision electronic parts, corrosion of metal parts, insulation failure, etc. are prevented. It is used for. That is, there is a need for a package having a gas barrier property that barriers oxygen and water vapor that permeate the packaging material.

  Therefore, metal foils such as aluminum and aluminum deposited films that are not affected by temperature, humidity, etc., or polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile ( PAN) and the like, and plastic films laminated or coated with these resins have been used favorably.

  However, packaging materials using metal foils such as aluminum and aluminum vapor-deposited films are excellent in gas barrier properties, but are opaque, so it is difficult not only to identify the contents through the packaging material, but also after use. However, it has the disadvantages that it must be treated as an incombustible material at the time of disposal, and that it cannot be inspected for foreign matter by a metal detector and cannot be heated in a microwave oven.

  In addition, a gas barrier resin film or a film coated with a gas barrier resin is highly temperature dependent and cannot maintain high gas barrier properties. Furthermore, PVDC and PAN after use have problems such as the possibility of causing harmful substances during disposal and incineration.

  Therefore, as a packaging material that overcomes these drawbacks, a gas barrier film in which an inorganic oxide such as aluminum oxide or silicon oxide is vapor-deposited on a transparent polymer film substrate has recently been put on the market.

  These gas barrier vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and are suitable as packaging materials having both transparency and gas barrier properties that cannot be obtained with metal foil or the like. The film on which silicon oxide SiOx is deposited is used as a food packaging film. Further, vapor deposition by a heating method using silicon oxide SiOx as a vapor deposition material has a very high film forming speed and high productivity.

  However, the silicon oxide SiOx (0 <x <2), which is a deposition material used here, is manufactured by vacuum deposition using silicon and silicon dioxide as raw materials, and thus has the following drawbacks. ing.

  Silicon oxide SiOx (0 <x <2), which is a material for vapor deposition produced by a vacuum vapor deposition method, is not a production method suitable for mass production, and thus has a problem of high material costs and high production costs. Further, the silicon oxide SiOx (0 <x <2) of this vapor deposition material has a density close to the true density and has a very dense structure.

  Therefore, when a gas barrier film is manufactured by vapor deposition of this vapor deposition material, the vaporized vapor deposition material is scattered as high-temperature particles due to the thermal shock caused by heating during vapor deposition or the pressure of gas generated from the inside. There is a problem that a phenomenon called splash occurs.

  When high-temperature particles reach the polymer film, pinholes and foreign matters are generated, resulting in a deterioration in gas barrier properties and poor appearance. Further, among the heating methods, particularly when heated by an electron gun, the above-described splash and foreign matter are more prominently generated by the deposition material receiving a larger thermal shock.

  On the other hand, a mixed vapor deposition material made of silicon and silicon dioxide is relatively inexpensive, but it is difficult to evaporate because it has a higher vapor pressure than silicon monoxide during heating, and it is a melt-type vapor deposition material. Therefore, a larger thermal shock is required, and the vapor deposition material is scattered and splash is likely to occur. In addition, the generation of oxygen gas due to the decomposition of silicon dioxide increases the pressure in the film formation chamber, which lowers the deposition rate, that is, reduces productivity. Furthermore, there is also a problem that causes the gas barrier property of the deposited film to be lowered due to the lowered deposited film density (Patent Document 1).

  Further, in Patent Document 1, although Si oxide is described as 100 to 250 parts by weight with respect to 100 parts by weight of Si, in this range, the ratio of oxygen to silicon atoms (O / Si) is 0. 6 to 1.1, and even in this state, it is not sufficient to suppress the occurrence of splash.

  Furthermore, in a mixed vapor deposition material composed of silicon and silicon dioxide, sufficient transparency is obtained with the ratio of the number of oxygen atoms to silicon (O / Si) set to prevent barrier deterioration due to oxygen gas generated from silicon dioxide. I can't get it. (Patent Document 2)

Japanese Patent No. 3191321 Japanese Patent No. 3267737

  The present invention is intended to solve the above-described problems of the prior art, and a deposition material containing silicon and silicon oxide that can suppress the occurrence of a splash phenomenon, and a film formed by heating deposition using the same. It aims at providing a transparent gas barrier vapor deposition film.

  In order to solve the above problems, the inventors have intensively studied and completed the present invention.

The invention according to claim 1 of the present invention is a heating type vapor deposition material in which metallic silicon and silicon oxide are mixed, and has a bulk density of 0.6 g / cm ³ or more and less than 2.0 g / cm ³ . In the range of deposition materials,
The ratio of the number of oxygen atoms to silicon (O / Si) is in the range of 1.2 to 2.0, and the silicon oxide is silicon dioxide containing at least 20% of crystal structure. It is a material for vapor deposition.

The invention according to claim 2 of the present invention is a heating type vapor deposition material in which a silicon-based mixture and a tin-based material are mixed, and has a bulk density of 0.6 g / cm ³ or more and less than 2.0 g / cm ^3. In the deposition material that is in the range of
The silicon-based mixture is made of a mixture of metal silicon and silicon oxide, the ratio of the number of oxygen atoms to silicon (O / Si) is in the range of 1.2 to 2.0, and the silicon The oxide is silicon dioxide containing a crystal structure of at least 20% or more,
The tin-based material is metal tin, tin oxide or a compound containing tin,
An evaporation material comprising 1 to 50% by weight of the tin-based material with respect to 100% by weight of the silicon-based mixture.

  The invention according to claim 3 of the present invention is a transparent gas barrier vapor-deposited film obtained by evaporating the vapor deposition material according to claim 1 by a heating method.

  The invention according to claim 4 of the present invention is a transparent gas barrier vapor-deposited film obtained by evaporating the vapor deposition material according to claim 2 by a heating method.

  The invention according to claim 5 of the present invention is the transparent gas barrier vapor-deposited film according to claim 3 or 4, wherein the heating method is an electron beam method.

  According to the vapor deposition material of the present invention, a splash phenomenon can be suppressed and a vapor deposition film having high gas barrier properties can be obtained even when an electron beam heating vapor deposition method with a high output is used to improve productivity.

It is sectional explanatory drawing which shows an example of the layer structure of the transparent gas barrier vapor deposition film of this invention. It is explanatory drawing which shows an example of the apparatus which manufactures the transparent gas barrier vapor deposition film of this invention.

  Embodiments of the present invention will be described below.

FIG. 1 is a cross-sectional explanatory view showing an example of the layer structure of the transparent gas barrier vapor deposition film of the present invention. The transparent gas barrier vapor-deposited film 8 is made of metal silicon (Si) and silicon oxide (SiOx) on the polymer film substrate 1, or metal tin (Sn) or tin oxide (SnO or SnO ₂ ), or these The inorganic oxide film 2 is formed by vacuum-depositing a vapor deposition material made of a mixture of compounds containing s. By doing in this way, the uniformity and gas barrier performance of the inorganic oxide film 2 can be obtained.

  As the film forming means, a heating vapor deposition method using an electron beam or a laser beam is preferable among the vacuum vapor deposition methods, and in particular, the electron beam heat vapor deposition method is a film formation rate or a temperature rising / falling temperature on an evaporation material which is an inorganic oxide. Is effective in that it can be performed in a short time.

The silicon oxide (SiOx) is preferably silicon dioxide (SiO ₂ ) containing at least 20% of a crystal structure. For this purpose, oxygen gas can be desorbed from silicon dioxide by an electron beam, and this oxygen gas can be reacted with metallic silicon, metallic tin, tin oxide or a compound containing them. In addition, the inorganic oxide film 2 may be formed on both surfaces of the polymer film substrate 1, may be multilayered, or may be an inorganic oxide film having a different composition on the front and back sides.

  The polymer film substrate 1 is not particularly limited, and a known one can be used. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene naphthalate, polyethylene terephthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol , Polymer film bases such as polycarbonate, polyethersulfone, acrylic, and cellulose (triacetylcellulose, diacetylcellulose, etc.), but not particularly limited.

  The polymer film substrate 1 is preferably a transparent film. A transparent gas barrier vapor deposition film can be formed. In addition, the thickness is not particularly limited, and a thickness range of 6 to 188 μm is preferable for practical use in consideration of workability such as vapor deposition.

  In general, the thickness of the inorganic oxide film 2 formed on the surface of the polymer film substrate 1 by the mixed vapor deposition material composed of metallic silicon and silicon dioxide is desirably in the range of 5 to 300 nm. Is appropriately selected.

  However, if the thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and sufficient barrier performance may not be exhibited. When the film thickness exceeds 300 nm, the film cannot retain flexibility, and there is a possibility that the inorganic oxide film 2 may crack due to external factors such as bending and tension after the film formation.

  A mixed material composed of metallic silicon and silicon oxide and metallic tin or tin oxide or a compound containing them used as a material for vapor deposition has a ratio of the number of atoms of oxygen and silicon (O / Si) and atoms of tin and silicon. By controlling the ratio of the number (Sn / Si), the weight of the metal tin or tin oxide mixed with the total weight of the metal silicon and silicon oxide, or the compound containing them, and the bulk density, etc. It is difficult to be destroyed by thermal shock, that is, the thermal shock resistance is improved and the splash phenomenon is suppressed.

  And in the case of vapor deposition by electron beam heating, by controlling the bulk density of the vapor deposition mixed material, the thermal conductivity is lowered so as not to become a dense structure, and silicon dioxide having a low thermal conductivity is added. By mixing, the occurrence of bumping due to a rapid temperature rise due to electron beam heating is suppressed, and the splash phenomenon is reduced.

  Further, when silicon dioxide is heated, oxygen gas is desorbed, and the heated silicon is also in the vicinity of oxygen gas generated from silicon dioxide, so that it undergoes an oxidation reaction without being bumped into SiOx vapor. In addition, the compound mainly composed of tin also becomes SnOy vapor, whereby a SiOx / SnOy composite film can be formed on the polymer film substrate 1. Moreover, it is thought that the splash is suppressed because the molten silicon dioxide remains on the surface layer of the vapor deposition material.

Regarding the vapor deposition material in which the metallic silicon and silicon oxide of the present invention are mixed, the ratio of the number of oxygen atoms to silicon (O / Si) needs to be in the range of 1.2 to 2.0. Further, a range of 1.2 to 1.8 is more preferable for a splashless process. When O / Si, which is in the description range of the cited document 1, is 1.1 or less, pinholes and appearance defects occur in the inorganic oxide film 2 formed on the polymer film substrate 1 due to splash, and O / Si Exceeds 2.0, the composition of the inorganic oxide film 2 approaches that of silicon dioxide (SiO ₂ ), resulting in barrier degradation.

The bulk density of the mixed vapor deposition material needs to be in the range of 0.6 g / cm ³ or more and less than 2.0 g / cm ³ . Furthermore, the range of 0.8-1.8 g / cm < ³ > is preferable. If the bulk density of the mixed vapor deposition material is 0.6 g / cm ³ or less, cracking or scattering of the vapor deposition material is likely to occur, and if the bulk density is 2.0 or more, more energy is required for evaporation of the material. For this reason, the heat load on the polymer film increases, the evaporation rate decreases, and the deposition rate decreases, that is, the productivity decreases.

  As the silicon oxide used here, it is necessary to use silicon dioxide having an X-ray crystal structure of at least 20% or more. For the measurement of the crystal part and the amorphous part of silicon dioxide, each peak was separated using an X-ray diffractometer (XRD), and the crystallinity was determined from the ratio of integrated intensity. When silicon dioxide having a crystallinity of less than 20%, that is, a crystal structure of less than 20% is used, the evaporation rate of the deposition material and the gas barrier property of the deposited film are inferior.

  Furthermore, vapor deposition materials made of metal silicon and silicon oxide are easy to mix when using the same particle size, and the temperature rising process of the vapor deposition material is simplified by using powder in the range of 1 to 100 μm. . This is presumably because the silicon, which is a metal, is uniformly mixed with the vapor deposition material, so that the material is likely to be warmed and the electron beam is not easily defocused.

  In addition, in the metal silicon and silicon oxide of the present invention, the ratio of metal tin or tin oxide or a compound containing them is preferably 1 to 50% by weight with respect to the total weight of the metal silicon and silicon oxide. A range of 1 to 30% by weight is preferred. If it is less than 1% by weight, the amount of SnOy contained in the vapor deposition material is small, so that SnOy cannot be mixed sufficiently uniformly into the vapor deposition film. On the other hand, if it exceeds 50% by weight, the gas barrier of the deposited film is lowered due to the occurrence of splash due to bumping derived from Sn having a low melting point and the lowering of the evaporation rate.

  The transparent gas barrier vapor-deposited film 8 of the present invention has a ratio of metal tin, tin oxide or a compound containing them in the range of 1 to 30% by weight with respect to the total weight of metal silicon and silicon oxide. By setting the specific bulk density, a transparent gas barrier vapor-deposited film having high barrier properties can be obtained without causing a splash phenomenon as compared with conventional vapor deposition materials.

  Further, a vapor deposition film obtained by using a vapor deposition material in which metal silicon, silicon oxide, metal tin, tin oxide or a compound containing them is mixed in the above ratio is a vapor deposition film composed only of metal silicon and silicon oxide. In comparison with the above, the average particle diameter of the deposited film can be grown 1.5 to 3.0 times. In the vapor deposition film with advanced grain growth, the gas barrier performance is improved because the grain boundary, which is assumed to be easy to pass gas such as water vapor, is reduced.

  FIG. 2 is an explanatory view showing an example of an apparatus for producing the transparent gas barrier vapor deposition film of the present invention. The vapor deposition apparatus 9 is located inside the vapor deposition chamber of the vacuum vapor deposition apparatus. Specifically, the vapor deposition apparatus 9 is an electron beam heating method, and has a film forming roll 3 on the upper side. The vapor deposition material 5 is heated and evaporated from the lower crucible 6 to form an inorganic oxide film 2 on the surface of the polymer film substrate 1, thereby forming a gas barrier vapor deposition film. . A indicates the traveling direction of the polymer film substrate 1. The transparent gas barrier vapor deposition film 8 can be produced by using a polymer film substrate having transparency.

  The crucible 6 is installed on a vapor deposition material moving carriage 7, an electron beam 4 emitted from an electron gun (not shown) is irradiated from above the crucible 6, and the vapor deposition material 5 in the crucible 6 is irradiated. Evaporate by heating. Further, the electron beam 4 is scanned or the evaporation material moving carriage 7 is moved so that the electron beam 4 is not irradiated only on the same position of the evaporation material 5.

  Specific examples of the present invention will be described below.

For metal silicon (Si), a powder having a diameter of 50 μm or less is 95% or more, and for silicon dioxide (SiO ₂ ), a powder having a crystal structure of 95% or more and a diameter of 50 μm or less is 95. % Or more was used. First, a mixed vapor deposition material made of metal silicon and silicon dioxide mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5 was produced. This mixed vapor deposition material was press-molded so that the bulk density was 1.0 g / cm ³ .

  Electron beam heating-type vacuum deposition equipment irradiates the mixed deposition material with the electron beam emitted from the electron gun and evaporates it, and adjusts the speed of the film-forming roll so that the inorganic oxide film has a thickness of about 50 nm. A gas barrier vapor-deposited film was produced by forming a film on a substrate (polyester film 12 μm).

The same metallic silicon as in Example 1 and silicon dioxide were mixed with 100% by weight of 20% by weight of silicon dioxide powder having no crystal structure and 80% by weight of silicon dioxide powder having a crystal structure, and having a diameter of 50 μm or less. A powder having 95% or more of was used. In the same manner as in Example 1, a mixed vapor deposition material composed of metal silicon and silicon dioxide mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5 was produced. Further, after press molding so that the bulk density is 1.0 g / cm ³ , an inorganic oxide film made of a silicon oxide film is similarly formed on the above polymer film substrate by an electron beam heating type vapor deposition apparatus. A gas barrier vapor-deposited film was produced.

In 100% by weight of the same metallic silicon as in Example 1 and silicon dioxide, 40% by weight of silicon dioxide powder having no crystal structure and 60% by weight of silicon dioxide powder having a crystal structure are mixed, and the diameter is 50 μm or less. A powder having 95% or more of was used. In the same manner as in Example 1, a mixed vapor deposition material composed of metal silicon and silicon dioxide mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5 was produced. Further, after press molding so that the bulk density is 1.0 g / cm ³ , an inorganic oxide film made of a silicon oxide film is similarly formed on the above polymer film substrate by an electron beam heating type vapor deposition apparatus. A gas barrier vapor-deposited film was produced.

The same metallic silicon as in Example 1 and silicon dioxide are mixed with 60% by weight of silicon dioxide powder having no crystal structure and 40% by weight of silicon dioxide powder having a crystal structure out of 100% by weight, and the diameter is 50 μm or less. A powder having 95% or more of was used. In the same manner as in Example 1, a mixed vapor deposition material composed of metal silicon and silicon dioxide mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5 was produced. Further, after press molding so that the bulk density is 1.0 g / cm ³ , an inorganic oxide film made of a silicon oxide film is similarly formed on the above polymer film substrate by an electron beam heating type vapor deposition apparatus. A gas barrier vapor-deposited film was produced.

Metallic silicon similar to Example 1 and silicon dioxide are mixed with 80% by weight of silicon dioxide powder having no crystal structure and 20% by weight of silicon dioxide powder having a crystal structure out of 100% by weight, and the diameter is 50 μm or less. A powder having 95% or more of was used. In the same manner as in Example 1, a mixed vapor deposition material composed of metal silicon and silicon dioxide mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5 was produced. Further, after press molding so that the bulk density is 1.0 g / cm ³ , an inorganic oxide film made of a silicon oxide film is similarly formed on the above polymer film substrate by an electron beam heating type vapor deposition apparatus. A gas barrier vapor-deposited film was produced.

20% by weight of metal tin (Sn) was added to the total weight of the metal silicon (Si) and silicon oxide (SiO ₂ ) mixed vapor deposition material prepared in Example 1. For Sn, a powder having a diameter of 50 μm or less of 95% or more was used, and this was press-molded so as to have a bulk density of 1.0 g / cm ^{3 in the same} manner as in Example 1, followed by electron beam heating in the same manner. An inorganic oxide film composed of a silicon oxide / tin oxide (SiOx / SnOx) composite film was formed on the above polymer film substrate by using a vapor deposition apparatus of the type to prepare a gas barrier vapor deposition film.

  Below, the comparative example of this invention is demonstrated.

<Comparative Example 1>
The same metallic silicon as in Example 1 and silicon dioxide powder having no crystal structure were mixed with silicon dioxide, and a powder having a diameter of 50 μm or less and 95% or more was used. As in Example 1, this was mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5, and pressed so that the bulk density was 1.0 g / cm ^3. After molding, similarly, an inorganic oxide film made of a silicon oxide film was formed on the above polymer film substrate with an electron beam heating type vapor deposition apparatus to produce a gas barrier vapor deposition film.

<Comparative example 2>
Powdered silicon monoxide (SiO) is used as a material for vapor deposition by vacuum vapor deposition, and this is press-molded so as to have a bulk density of 1.0 g / cm ^{3 in the same} manner as in Example 1, followed by electron beam heating in the same manner. An inorganic oxide film made of silicon oxide was formed on the polymer film substrate with a vapor deposition apparatus of the type to produce a gas barrier vapor deposition film.

<Comparative Example 3>
The same metal silicon and silicon dioxide powder as in Example 1 were mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.0. This was press-molded to a bulk density of 1.0 g / cm ³ in the same manner as in Example 1, and an inorganic oxide film made of a silicon oxide film was similarly formed by the electron beam heating type vapor deposition apparatus. A gas barrier vapor deposition film was produced by forming a film thereon.

<Comparative Example 4>
The same metal silicon and silicon dioxide powder as in Example 1 were mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5. This was press-molded to a bulk density of 2.0 g / cm ³ in the same manner as in Example 1, and then an inorganic oxide film made of a silicon oxide film was similarly formed by the electron beam heating type vapor deposition apparatus. A gas barrier vapor deposition film was produced by forming a film thereon.

<Comparative Example 5>
The same metal silicon and silicon dioxide powder as in Example 1 were mixed so that the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) was 1.5. Furthermore, 50% by weight of metallic tin was mixed with respect to the total weight of the mixed material. This was press molded to a bulk density of 1.0 g / cm ³ in the same manner as in Example 1, and then similarly an inorganic oxide comprising a silicon oxide / tin oxide (SiOx / SnOy) composite film by an electron beam heating type vapor deposition apparatus. The film was formed on the above polymer film substrate to produce a gas barrier vapor deposition film.

<Comparative Example 6>
The same mixed vapor deposition material as in Example 1 was used. This was press-molded to a bulk density of 1.0 g / cm ³ in the same manner as in Example 1, and then oxygen was introduced when vapor-deposited by an electron beam heating type vapor deposition apparatus in the same manner, and silicon oxide / tin oxide (SiOx · An inorganic oxide film composed of a SnOy) composite film was formed on the above polymer film substrate to produce a gas barrier vapor deposition film.

  About the gas-barrier vapor deposition film of Examples 1-6 and Comparative Examples 1-6, generation | occurrence | production of the splash was checked with the following method, and the water-vapor-permeation rate was measured. Further, the ratio of the number of atoms of oxygen and silicon (O / Si) and the ratio of the total number of atoms of oxygen, silicon and tin {O / (Si + Sn) ratio} of the inorganic oxide film deposited by evaporating the material for mixed vapor deposition Was measured. The results are shown in Tables 1-3.

  The evaluation method was performed by the following method.

<Water vapor permeability>
The water vapor permeability of the gas barrier vapor-deposited films of Examples 1 to 8 and Comparative Examples 1 to 5 was measured in a 40 ° C. and 90% RH atmosphere using a water vapor permeability measuring device (MOCON PERMATRAN 3/21 manufactured by Modern Control). .

<Splash>
The gas barrier vapor-deposited films of Examples 1 and 6 to 8 and Comparative Examples 2 to 5 were each visually examined for the presence of pinholes and foreign matters due to splash for a width of 500 mm and a length of 100 m. The case where there was no pinhole or foreign matter due to splash was marked as ◯, the number of pinholes or foreign matter due to splash was 1 to 10, and the case where there were 11 or more pinholes or foreign matter due to splash was marked as x.

<O / Si and O / (Si + Sn) of the deposited film>
The ratio of the number of atoms of oxygen and silicon (O / Si) in the vapor deposition films of the gas barrier vapor deposition films of Examples 6 and 8 and Comparative Example 5 and the ratio of the total number of atoms of oxygen, silicon and tin {O / (Si + Sn ) Ratio} was measured by the following method. Sampling method: The polymer film substrate on which the inorganic oxide film was formed was cut into 10 mm × 10 mm squares.

  Measuring instrument and measuring method: The composition of the inorganic oxide film was analyzed by an X-ray photoelectron spectrometer (ESCA). The composition analysis is repeated three times or more in the depth direction of the deposited film with Ar ions, the average is obtained, and the ratio of the number of atoms of oxygen and silicon (O / Si) and the ratio of the total number of atoms of oxygen, silicon and tin { O / (Si + Sn) ratio} was calculated.

<Average particle size>
Measuring instrument and measuring method: The surface of the inorganic oxide film was observed at a magnification of 200,000 times with a scanning electron microscope (SEM). The diameter of the particle which exists in a 100 nm x 100 nm angle | corner was measured, the diameter of the particle | grain diameter was calculated | required, and it computed as an average particle diameter.

<Evaluation results>
From Table 1, even if the content of the crystal structure of silicon dioxide (SiO ₂ ) contained in the vapor deposition material is reduced to 20% as in Examples 1 to 5, there is a large difference between the evaporation rate and the water vapor transmission rate. Although not seen, if silicon dioxide containing no crystal structure is used as the silicon dioxide contained in the vapor deposition material, the evaporation rate and water vapor permeability are lowered. For this reason, it was found that the silicon dioxide used for the vapor deposition material preferably has a crystal structure of 20% or more.

  From Table 2, the occurrence of splash was confirmed from Comparative Examples 2 and 3, whereas the other Examples 1 and 6 showed no splash. This means that the splash is suppressed by the ratio (O / Si) of the oxygen, the number of atoms, and the number of silicon atoms in the evaporation material. The splash was confirmed from Comparative Example 4 because the bulk density was high and the beam was difficult to enter, and the molten material on the surface bumped. Moreover, it is thought that the water vapor permeability was deteriorated because the film formation rate was slow and a heat load was applied on the polymer film substrate.

Further, by adding metal tin (Sn) to the vapor deposition material of Example 1 from Example 6, a remarkable improvement in water vapor barrier properties is observed. The water vapor permeability of an inorganic oxide film made of a mixed vapor deposition material of silicon and silicon dioxide or an inorganic oxide film made of a vapor deposition material of silicon monoxide is about ^{2 to 3} g / m ² · day, whereas Example 6 An inorganic oxide film made of a mixed vapor deposition material with the addition of metallic tin (Sn) has a water vapor permeability of 1 g / m ² · day or less by being a composite film of SiOx and SnOy, and has a water vapor barrier property. Is thought to have improved. On the other hand, in the vapor deposition composite film of Comparative Example 5 in which metal tin (Sn) was added excessively, the ratio of the number of tin atoms to the number of silicon atoms (Sn / Si) was 0.3 or more, and the water vapor permeability was Decrease significantly. Further, in the vapor-deposited composite film into which oxygen is introduced in Comparative Example 6, when the ratio of the total number of atoms of oxygen, silicon, and tin {O / (Si + Sn) ratio} is 1.90, x and y of SiOx and SnOy are Since the value approaches 2.0, the barrier property deteriorates.

DESCRIPTION OF SYMBOLS 1 ... Polymer film base material 2 ... Inorganic oxide film 3 ... Film-forming roll 4 ... Electron beam 5 ... Deposition material 6 ... Crucible 7 ... Deposition material movement Cart 8 ... Transparent gas barrier vapor deposition film 9 ... Vapor deposition apparatus A ... Direction of travel of polymer film substrate

Claims (5)

In a heating method vapor deposition material in which metallic silicon and silicon oxide are mixed, and the bulk density is in the range of 0.6 g / cm ³ or more and less than 2.0 g / cm ³ ,
The ratio of the number of oxygen atoms to silicon (O / Si) is in the range of 1.2 to 2.0, and the silicon oxide is silicon dioxide containing at least 20% of crystal structure. Vapor deposition material. A vapor deposition material of a heating method in which a silicon-based mixture and a tin-based material are mixed, wherein the bulk density is in a range of 0.6 g / cm ³ or more and less than 2.0 g / cm ³ .
The silicon-based mixture is made of a mixture of metal silicon and silicon oxide, the ratio of the number of oxygen atoms to silicon (O / Si) is in the range of 1.2 to 2.0, and the silicon The oxide is silicon dioxide containing a crystal structure of at least 20% or more,
The tin-based material is metal tin, tin oxide or a compound containing tin,
An evaporation material comprising 1 to 50% by weight of the tin-based material with respect to 100% by weight of the silicon-based mixture.   A transparent gas barrier vapor deposition film, wherein the vapor deposition material according to claim 1 is vapor deposited by a heating method.   A transparent gas barrier vapor-deposited film, wherein the vapor deposition material according to claim 2 is vapor-deposited by a heating method.   The transparent gas barrier vapor deposition film according to claim 3 or 4, wherein the heating method is an electron beam method.