JP6944664B2 - Barrier film - Google Patents

Description

The present invention relates to a barrier film, and more particularly, a barrier property including a resin base material, a first chemical vapor deposition layer, an atomic layer deposition film, and a second chemical vapor deposition layer in this order. Regarding film.

In recent years, as a barrier material against oxygen or water vapor, inorganic oxides such as silicon oxide and aluminum oxide have been formed on a film substrate by a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, or the like. The transparent gas barrier film is attracting attention. The conventional barrier film laminated with polyvinylidene chloride is excellent in gas blocking property, but there is a problem that chlorine is generated when the packaging material is disposed of. In addition, a barrier film laminated with aluminum foil or the like has excellent gas blocking properties, but is opaque, so it should be used in applications where visibility of the contents is required in order to avoid accidents due to misidentification of the contents. I can't.

For example, when a SiNx film is formed by plasma CVD using monosilane and ammonia, there is a problem that the refractive index of the film is high and the transmittance is low, although the barrier property is high.
In plasma CVD, a method of forming a SiOx film or SiOxCy using an organosilicon compound such as HMDSO can be considered, but the barrier property cannot be improved so much with a thin film, or the barrier film becomes yellowish when the film thickness is increased. There was a problem that the transmittance became low due to the problem.

In addition, there is a technique called atomic layer deposition as a technique for obtaining a barrier property with a thin film, and when AlOx is formed by this method, it is possible to obtain a barrier property of ^{10-4 units with a film thickness of about 20 nm.} However, there is a problem that it may deteriorate just by touching it during handling and its moisture and heat resistance is very low. It is considered that the low moisture and heat resistance is due to the hydroxylation of the AlOx film under high temperature and high humidity.

Further, Patent Document 1 describes a gas barrier having a polymer film / adhesive layer (hydrolyzed product of acrylic resin and tetraethoxysilane) / ceramic film by atomic layer deposition method / protective layer (hydrolyzed product of tetraethoxysilane). In the film, a method of slowing the permeation of water vapor into the ceramic film and each interface by using a protective layer has been proposed.
Patent Document 2 proposes a gas-barrier laminate having a structure of a plastic film base material, a base layer by CVD, and a gas barrier layer by an atomic layer deposition method.
Patent Document 3 proposes that a gas barrier film having a structure of a base material / PVD layer / layer by an atomic layer deposition method / polysilazane layer suppresses a decrease in barrier property at high temperature and high humidity.
Patent Document 4 proposes a gas barrier film having a structure of a base material / an adhesive layer (a hydrolyzate of an acrylic resin and tetraethoxysilane) / a ceramic film by an atomic layer deposition method / a protective layer (a hydrolyzate).

Japanese Unexamined Patent Publication No. 2011-173261 Japanese Unexamined Patent Publication No. 2011-241421 Japanese Unexamined Patent Publication No. 2015-3464 JP-A-2015-77804

However, the present inventors have found that the inventions described in Patent Documents 1 to 4 have the following technical problems.
Since the protective layer in the gas barrier film described in Patent Document 1 has a lower barrier property than the barrier layer formed by dry film formation, it is insufficient as a layer for protecting the layer by the atomic layer deposition method. Further, since the aging of the hydrolyzate usually takes about 3 to 5 days, there is a drawback that the lead time becomes long.
In the gas barrier laminate described in Patent Document 2, the layer by the atomic layer deposition method was not protected and was easily deteriorated by high temperature and high humidity or contact.
In order to produce the gas barrier film described in Patent Document 3, there is a concern that equipment capable of forming at least three types of films is required, resulting in high cost. Further, in the examples, since the bleed-out prevention layer and the smooth layer are further provided on the base material, it is necessary to substantially provide five layers on the base material in order to obtain the desired performance.
The gas barrier film described in Patent Document 4 has a drawback that the lead time becomes long because the aging of the hydrolyzate usually takes about 3 to 5 days.
Therefore, there is still a demand for a barrier film having excellent transparency, moisture resistance, heat resistance, and weather resistance.

As a result of diligent studies to solve the above problems, the present inventors have conducted a first chemical vapor deposition layer and a second chemical vapor deposition on a resin substrate by a chemical vapor deposition method (CVD method). It has been found that by forming a layer, it is possible to provide a barrier film having excellent transparency, moisture resistance, heat resistance and weather resistance. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention.
A barrier film comprising a resin base material, a first chemical vapor deposition layer, an atomic layer deposition film, and a second chemical vapor deposition layer in this order.
The first chemical vapor deposition layer contains silicon, oxygen and carbon.
The atomic layer deposition film contains aluminum and oxygen and contains
The second chemical vapor deposition layer contains silicon, oxygen and carbon and contains
In the first chemical vapor deposition layer and the second chemical vapor deposition layer, the ratio of carbon to 100% of the total of the three elements of silicon, oxygen, and carbon is 0.1% or more and less than 15%. can be,
A third chemical vapor deposition layer is further provided between the resin substrate and the first chemical vapor deposition layer, and the third chemical vapor deposition layer contains silicon, oxygen and carbon, and is silicon. A barrier film having a carbon content of 15% or more and 40% or less with respect to a total of 100% of the three elements of, oxygen, and carbon is provided.
In the embodiment of the present invention, the first chemical vapor deposition layer and the second chemical vapor deposition layer further contain nitrogen, and the total of four elements of silicon, oxygen, carbon, and nitrogen is 100%. , The ratio of nitrogen is preferably 1% or less.
In the aspect of the present invention, it is preferable that the barrier film has an easy-adhesion layer on the resin base material, and the first chemical vapor deposition layer is not directly provided on the easy-adhesion layer. ..
In the aspect of the present invention, it is preferable that the layer containing the lubricant is not provided on at least one surface of the resin base material.
In the aspect of the present invention, the water vapor permeability is preferably 1.0 × ^10-2 g / m ² / day or less.
In the aspect of the present invention, the total light transmittance is preferably 85% or more.
In the embodiment of the present invention, the water vapor transmittance after storage at 85 ° C. and 85% RH for 120 hours ^{is preferably 1 g / m 2} / day or less.
In the aspect of the present invention, it is preferable that the water vapor transmittance after the irradiation test for 120 hours with a xenon weather meter is 1 g / m ² / day or less in accordance with ISO 4892-2.

According to the present invention, it is possible to provide a barrier film having excellent transparency and excellent water vapor barrier property even after storage in a high temperature and high humidity environment or after irradiation with a xenon lamp for a long time. Such a barrier film can be suitably used for packaging of foods, packaging of medical medicines, substrates of electronic products, etc., which require visibility.

It is the schematic sectional drawing which showed one Embodiment of the barrier film of this invention. It is the schematic sectional drawing which showed one Embodiment of the barrier film of this invention.

<Barrier film>
The barrier film according to the present invention is a barrier film including a resin base material, a first chemical vapor deposition layer, an atomic layer deposition film, and a second chemical vapor deposition layer in this order. The barrier film may further include a third chemical vapor deposition layer between the resin substrate and the first chemical vapor deposition layer.

The barrier film has excellent water vapor barrier properties and has a water vapor permeability of preferably 1.0 × 10 ^-2 g / m ² / day or less, more preferably 5.0 × 10 ^-3 g / m ² / day. It is less than or equal to day, more preferably 1.0 × 10 ^-3 g / m ² / day or less, and even more preferably 5.0 × 10 ^-4 g / m ² / day or less. If the water vapor transmission rate satisfies the above numerical range, it can be used as a packaging material even in applications requiring a high degree of water vapor barrier property. The temperature of the water vapor transmission rate is 40, using a water vapor transmission rate measuring machine (MOCON: PERMATRAN), JIS K7129B, or Teknolux DELTAPARM, ISO 15106-5. It can be measured in an environment of ° C. and humidity of 90%.

^{The barrier film has a water vapor permeability of preferably 1 g / m 2} / day or less after being stored for 120 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and more preferably 1.0 × 10 ^-1 g /. It is m ² / day or less, more preferably 5.0 × 10 ^-2 g / m ² / day or less, still more preferably 1.0 × 10 ^-2 g / m ² / day or less, and most preferably. It is 1.0 × 10 ^-3 g / m ² / day or less. If the water vapor transmission rate after storage under the above conditions satisfies the above numerical range, it can be used as a packaging material even in applications exposed to a high temperature and high humidity environment.

^{The barrier film has a water vapor transmission rate of preferably 1 g / m 2} / day or less, more preferably 1.0, after an irradiation test for 120 hours with a xenon weather meter in accordance with ISO 4892-2. × 10 ^-1 g / m ² / day or less, more preferably 5.0 × 10 ^-2 g / m ² / day or less, still more preferably 1.0 × 10 ^-2 g / m ² / day or less. Most preferably, it is 1.0 × 10 ^-3 g / m ² / day or less. If the water vapor transmission rate after storage under the above conditions satisfies the above numerical range, it can be used as a packaging material even in applications exposed to a high temperature and high humidity environment.

The barrier film has excellent light transmittance, and the total light transmittance is preferably 85% or more, more preferably 88% or more, and further preferably 90% or more. If the total light transmittance satisfies the above numerical range, the visibility of the contents is excellent when used as a packaging material. The total light transmittance can be measured in accordance with JIS K7361 using HAZE METER HM-150 manufactured by Murakami Daylighting Research Institute Co., Ltd.

The barrier film is excellent in light transmission and has a haze of preferably 5% or less, more preferably 3% or less, still more preferably 1% or less. If the haze satisfies the above numerical range, the visibility of the contents is excellent when used as a packaging material. The haze can be measured in accordance with JIS K7136 using HAZE METER HM-150 manufactured by Murakami Daylighting Research Institute Co., Ltd.

The layer structure of the barrier film will be described with reference to the drawings. The barrier film 10 shown in FIG. 1 has a resin base material 11, a first chemical vapor deposition layer 12, an atomic layer deposition film 13, and a second chemical vapor deposition layer 14 on the resin base material 11. And are prepared in this order. Further, the barrier film 20 shown in FIG. 2 has a resin base material 11, a third chemical vapor deposition layer 15, a first chemical vapor deposition layer 12, and an atomic layer deposition on the resin base material 11. The film 13 and the second chemical vapor deposition layer 14 are provided in this order. Hereinafter, each layer constituting the barrier film of the present invention will be described.

<Resin base material>
The resin base material constituting the barrier film according to the present invention is not particularly limited as long as it can support the following chemical vapor deposition layer, and various known resin base materials can be used.
For example, a film of a thermosetting resin or a thermoplastic resin can be used.

Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, polyimide and the like. Examples of the thermoplastic resin include polyolefins such as polyethylene, polypropylene, poly4-methyl-1-pentene, and polybutene, polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, nylon-6, nylon-66, and the like. And polyamide such as polymethoxylen adipamide, polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin or a mixture thereof. Be done. In particular, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyimide, are preferable. The resin base material made of these thermoplastic resins may be a single layer or a laminate made of two or more kinds of thermoplastic resins, depending on the use of the barrier film. Further, in order to improve the adhesiveness of these resin substrates with the following chemical vapor deposition layers, the surface thereof is, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coating treatment, frame. Surface activation treatment such as treatment may be performed.

<Atomic layer deposition film>
The atomic layer deposition film constituting the barrier film according to the present invention is an inorganic oxide film formed by the atomic layer deposition method (ALD method).

The atomic layer deposition film in the present invention preferably contains aluminum and oxygen, and the inorganic oxide film preferably contains _{Al 2} O _3. It is more preferable to use TMA (trimethylaluminum) in consideration of the reactivity of the material. An intermediate oxide such as AlOx may be contained by adjusting the introduction time of each gas, the film forming temperature, and the pressure at the time of film formation.

In the atomic layer deposit film, the ratio of aluminum is preferably 30% or more and 42% or less, and more preferably 32% or more and 40% or less, based on 100% of the total of the three elements of aluminum, oxygen, and carbon. , More preferably 34% or more and 38% or less, and the proportion of oxygen is preferably 50% or more and 70% or less, more preferably 54% or more and 66% or less, and even more preferably 56% or more and 64. % Or less, and the carbon ratio is preferably 0.1% or more and less than 10%, more preferably 0.5% or more and 9% or less, and further preferably 1% or more and 8% or less.

The atomic layer deposition film, the film density of inorganic oxide, preferably at 2.50 g / cm ³ or more 3.00 g / cm ³ or less, more preferably 2.55 g / cm ³ or more 2.95 g / cm ³ or less It is even more preferably 2.60 g / cm ³ or more and 2.90 g / cm ³ or less. When the film density of the inorganic oxide is in the above range, it ^{is lower than the film density by the conventional PVD method (about 3.5 to 3.6 g / cm 3} ), so that the possibility of the film cracking can be reduced. The film density of the inorganic oxide can be adjusted to a desired range by adjusting the film transport rate, the film formation temperature, and the like in the atomic layer deposition method. For the film density, an X-ray intensity profile was measured using "ATX-G" manufactured by Rigaku Co., Ltd. under the conditions of anti-catalyst: Cu, wavelength: 1.5405 Å, output: 50 kV, 300 mA, and this X-ray intensity was measured. It can be calculated by optimizing the simulation parameters using simulation software (“DX-RR3” manufactured by Rigaku Co., Ltd.) so as to match the profile.

In the atomic layer deposition film, the refractive index of the inorganic oxide film is preferably 1.50 or more and 1.65 or less, and more preferably 1.55 or more and 1.64 or less. If the refractive index is within the above range, a resin base material of a plastic film having a low refractive index such as biaxially stretched polypropylene (refractive index: 1.47) or biaxially stretched polyethylene terephthalate (refractive index: 1.64). Even when laminated to, it is difficult for reflection to occur in the boundary layer, and the occurrence of a rainbow pattern due to interference can be suppressed. The refractive index of the inorganic oxide film can be adjusted to a desired range by adjusting the film transport rate, the film formation temperature, and the like in the atomic layer deposition method. The refractive index can be measured using an ellipsometer (Mizojiri Optical Co., Ltd., DVA-36L, He-Ne laser light (632.8 nm)).

<Chemical vapor deposition layer>
The chemical vapor deposition layer constituting the barrier film according to the present invention is a vapor deposition film formed by a chemical vapor deposition method (CVD method). In the present invention, the chemical vapor deposition layer is a barrier film because it is easier to form a thick-film vapor deposition layer and has excellent flexibility as compared with the vapor deposition film obtained by the physical vapor deposition method (PVD method). It is more suitable as a vapor deposition layer.

The barrier film includes chemical vapor deposition layers on both sides of the atomic layer deposition film. By providing chemical vapor deposition layers on both sides of the atomic layer deposition film, the atomic layer deposition film is protected and has gas barrier properties even after storage in a high temperature and high humidity environment or after long-term irradiation with a xenon lamp. An excellent barrier film can be obtained. The chemical vapor deposition layers on both sides of the atomic layer deposition film are the first chemical vapor deposition layer and the second chemical vapor deposition layer in this order from the resin substrate side.

The first chemical vapor deposition layer and the second chemical vapor deposition layer both contain silicon, oxygen, and carbon. By forming the first chemical vapor deposition layer and the second chemical vapor deposition layer as a vapor deposition film containing the same element, the adhesion between the two can be improved and the water vapor barrier property can be improved.

In the first and second chemical vapor vapor deposition layers, the ratio of silicon is preferably 27% or more and 40% or less, more preferably 29, with respect to a total of 100% of the three elements of silicon, oxygen, and carbon. % Or more and 37% or less, still more preferably 31% or more and 35% or less, and the oxygen ratio is preferably 55% or more and 75% or less, more preferably 60% or more and 70% or less, and further. More preferably 62% or more and 68% or less, the proportion of carbon is preferably 0.1% or more and less than 15%, more preferably 0.5% or more and 12% or less, still more preferably 1%. More than 8% or less.
Further, in the first and second chemical vapor deposition layers, the ratio of nitrogen is preferably 1% or less, more preferably 1% or less, based on a total of 100% of the four elements of silicon, oxygen, carbon, and nitrogen. It is 0.5% or less. Since the proportion of nitrogen in the first and second chemical vapor deposition layers is low, the refractive index can be kept low.

The barrier film may further include a third chemical vapor deposition layer between the resin substrate and the first chemical vapor deposition layer. The third chemical vapor deposition layer contains silicon and oxygen. The carbon ratio in the third chemical vapor deposition layer is preferably higher than the carbon ratio in the first chemical vapor deposition layer. By satisfying such conditions, damage during film formation can be reduced, and even if there is further damage in a high temperature and high humidity environment or under xenon lamp irradiation, a state having excellent water vapor barrier properties can be maintained.

In the third chemical vapor vapor deposition layer, the ratio of silicon is preferably 24% or more and 36% or less, and more preferably 26% or more and 34%, based on a total of 100% of the three elements of silicon, oxygen, and carbon. % Or less, more preferably 28% or more and 32% or less, and the proportion of oxygen is preferably 36% or more and 60% or less, more preferably 38% or more and 54% or less, and even more preferably. It is 40% or more and 48% or less, and the ratio of carbon is preferably 15% or more and 40% or less, preferably 16% or more and 38% or less, and more preferably 17% or more and 35% or less.

The thickness of the first and second chemical vapor deposition layers is preferably 10 nm or more and less than 500 nm, more preferably 30 nm or more and 300 nm or less, and further preferably 50 nm or more and 200 nm or less.
The thickness of the third chemical vapor deposition layer is preferably 10 nm or more and 500 nm or less, more preferably 30 nm or more and 300 nm or less, and further preferably 50 nm or more and 200 nm or less.
By providing the chemical vapor deposition layer having the above thickness, the barrier film has excellent water vapor barrier property even after storage in a high temperature and high humidity environment. The thickness of the chemical vapor deposition layer can be adjusted to a desired range by adjusting the film formation time or film transport speed during vapor deposition by the CVD method.

<Other layers>
The barrier film may have an easy-adhesion layer on the resin substrate. However, from the viewpoint of moisture resistance and heat resistance, when the easy-adhesion layer is provided on the resin base material, it is preferable that the first chemical vapor deposition layer is not directly provided on the easy-adhesion layer. Further, from the viewpoint of moisture resistance and heat resistance, it is preferable that the layer containing the lubricant is not provided on at least one surface of the resin base material.

<Manufacturing method of barrier film>
In the method for producing a barrier film according to the present invention, the chemical vapor deposition layer can be formed as follows. A film-forming monomer gas containing one or more organic silicon compounds is used as a raw material on a resin base material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is further used as an oxygen supply gas. The first to third chemical vapor deposition layers containing silicon oxide can be formed by using a gas or the like and using a plasma chemical vapor deposition method using a plasma generator or the like.

In the above, as the plasma generator, for example, a conventionally known plasma generator such as a high frequency plasma, a pulse wave plasma, or a microwave plasma can be used. In the present invention, in order to obtain a highly active and stable plasma, it is desirable to use a generator by a high frequency plasma method.

As a mixing ratio of each gas component of the film-forming mixed gas composition, for example, a film-forming monomer gas:
A mixed gas composition for film formation or the like having a gas composition ratio of oxygen gas: inert gas = 1: 0 to 50: 0 to 20 (unit: sccm) can be used. By using such a mixed gas composition for film formation, silicon oxide is mainly used, and at least one kind of compound composed of one or more kinds of elements such as carbon, hydrogen, silicon and oxygen is chemically bonded to the silicon oxide. The vapor-deposited film contained therein can be formed by the above. By adjusting the mixing ratio of each gas component of the mixed gas composition for film formation, the proportions of silicon, oxygen, and carbon contained in the first to third chemical vapor deposition layers can be appropriately adjusted.

Examples of the organic silicon compound constituting the film-forming monomer gas include 11.3.3-tetramethyldisiloxane, hexamethyldisiloxane (HMDSO), vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, and methylsilane. , Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, Others can be used. Among these organic silicon compounds, it is particularly preferable to use 11.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material from the viewpoints of handleability, characteristics of the formed continuous film, and the like. Further, as the inert gas, for example, argon gas, helium gas or the like can be used.

In addition, the atomic layer deposition film can be formed by the atomic layer deposition method as follows. First, the atomic layer deposition method is a method of depositing atomic layers one by one by alternately introducing two or more kinds of gases (first gas and second gas) onto a substrate. More specifically, first, a first gas is introduced onto the base material to form a gas molecular layer (monatomic layer). The first gas is then purged by introducing an inert gas. The gas molecular layer of the formed first gas is not purged even if an inert gas is introduced by chemical adsorption. Next, the gas molecular layer formed by introducing the second gas is oxidized to form an inorganic film. Finally, by introducing the inert gas, the second gas is purged and one cycle of the atomic layer deposition method is completed. By repeating the above cycle, atomic layers are deposited one by one to form a first gas barrier layer having a predetermined film thickness. In the atomic layer deposition method, an inorganic film can be formed including a shaded portion regardless of the unevenness of the surface of the substrate.

The film formation temperature requires activation of the substrate surface for adsorption of gas molecules to the substrate. Therefore, the film formation temperature is preferably a high temperature to some extent, and may be appropriately adjusted within a range not exceeding the glass transition temperature or the decomposition start temperature of the plastic substrate of the base material. When a plastic base material is used, the temperature inside the reactor is usually about 50 to 200 ° C. The deposition rate in one cycle is usually 0.01 to 0.3 nm, and the desired film thickness is obtained by repeating the film formation cycle.

When the inorganic oxide is aluminum oxide, the first gas can be a gas obtained by vaporizing an aluminum compound, and the second gas can be an oxidizing gas. The inert gas is a gas that does not react with the first gas and / or the second gas.

The aluminum compound is not particularly limited as long as it contains aluminum and can be vaporized. Specific examples of the aluminum compound include trimethylaluminum (TMA), triethylaluminum (TEA), and trichloroaluminum.

As the oxidizing gas, H ₂ O is used, and a method of oxidizing by introducing oxygen and then creating a plasma is adopted.

<Use>
The barrier film according to the present invention can be applied to products in various fields that require a high degree of barrier property. For example, it can be used for packaging products, electric / electronic products such as solar cells, organic light emitting diodes, and display devices.

<Packaging material>
The barrier film according to the present invention can be suitably used as a packaging material. For example, it can be used for pharmaceuticals, cosmetics, chemicals, foods and drinks, and the like. Since the barrier film has excellent transparency and excellent water vapor barrier property even after storage in a high temperature and high humidity environment, visibility of the contents and high water vapor barrier property are required. , Can be suitably used as a packaging material.

<Electrical and electronic products>
The barrier film according to the present invention can be particularly preferably used as a base material / cover material for electrical / electronic products. For example, it can be used for organic solar cells and organic light emitting diodes. The barrier film has excellent transparency and excellent water vapor barrier property even after storage in a high temperature and high humidity environment or an environment exposed to ultraviolet rays, so that it has high light transparency and high degree of light transmission. It can be particularly preferably used as a base material / cover material for electric / electronic products that require water vapor barrier properties.

<Other aspects>
The present inventors have found that the inventions described in Patent Documents 1 to 4 have the following technical problems.
Since the protective layer in the gas barrier film described in Patent Document 1 has a lower barrier property than the barrier layer formed by dry film formation, it is insufficient as a layer for protecting the layer by the atomic layer deposition method. Further, since the aging of the hydrolyzate usually takes about 3 to 5 days, there is a drawback that the lead time becomes long.
In the gas barrier laminate described in Patent Document 2, the layer by the atomic layer deposition method was not protected and was easily deteriorated by high temperature and high humidity or contact.
In order to produce the gas barrier film described in Patent Document 3, there is a concern that equipment capable of forming at least three types of films is required, resulting in high cost. Further, in the examples, since the bleed-out prevention layer and the smooth layer are further provided on the base material, it is necessary to substantially provide five layers on the base material in order to obtain the desired performance.
The gas barrier film described in Patent Document 4 has a drawback that the lead time becomes long because the aging of the hydrolyzate usually takes about 3 to 5 days.
Therefore, there is still a demand for a barrier film having excellent transparency, moisture resistance, heat resistance, and weather resistance.
As a result of diligent studies to solve the above problems, the present inventors have conducted a first chemical vapor deposition layer and a second chemical vapor deposition on a resin substrate by a chemical vapor deposition method (CVD method). It has been found that by forming a layer, it is possible to provide a barrier film having excellent transparency, moisture resistance, heat resistance and weather resistance. Other aspects of the invention have been completed on the basis of such findings.

That is, according to another aspect of the present invention.
A barrier film comprising a resin base material, a first chemical vapor deposition layer, an atomic layer deposition film, and a second chemical vapor deposition layer in this order.
The first chemical vapor deposition layer contains silicon and oxygen and contains
The atomic layer deposition film contains aluminum and oxygen and contains
A barrier film is provided in which the second chemical vapor deposition layer contains silicon and oxygen.
In another aspect of the present invention, in the first chemical vapor deposition layer and the second chemical vapor deposition layer, nitrogen is added to a total of 100% of the four elements of silicon, oxygen, carbon, and nitrogen. The ratio is preferably 1% or less.
In another aspect of the present invention, in the first chemical vapor deposition layer and the second chemical vapor deposition layer, the ratio of carbon to 100% of the total of the three elements of silicon, oxygen, and carbon is It is preferably 0.1% or more and less than 15%.
In another aspect of the invention, the barrier film further comprises a third chemical vapor deposition layer between the resin substrate and the first chemical vapor deposition layer, the third chemistry. It is preferable that the vapor deposition layer contains silicon and oxygen and has a carbon content of 15% or more and 40% or less.
In another aspect of the present invention, the barrier film has an easy-adhesion layer on the resin substrate, and the first chemical vapor deposition layer is not directly provided on the easy-adhesion layer. Is preferable.
In another aspect of the present invention, it is preferable that the layer containing the lubricant is not provided on at least one surface of the resin base material.
In another aspect of the present invention, the barrier film preferably has a water vapor permeability of 1.0 × ^10-2 g / m ² / day or less.
In another aspect of the present invention, the barrier film preferably has a total light transmittance of 85% or more.
In another aspect of the present invention, the barrier film preferably has a water vapor permeability of 1 g / m ² / day or less after being stored at 85 ° C. and 85% RH for 120 hours.
In another aspect of the present invention, the barrier film preferably has a water vapor transmittance of 1 g / m ² / day or less after an irradiation test for 120 hours with a xenon weather meter.
According to another aspect of the present invention, it is possible to provide a barrier film having excellent transparency and excellent water vapor barrier property even after storage in a high temperature and high humidity environment or after long-term irradiation with a xenon lamp. Can be done. Such a barrier film can be suitably used for packaging of foods, packaging of medical medicines, substrates of electronic products, etc., which require visibility.

<Manufacturing of barrier film>
[Example 1]
(Film layer configuration: PET / CVD-A / ALD / CVD-A)
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 50 μm, with an easy-adhesion layer on one side) was prepared as a resin base material. A first chemical vapor deposition layer under the following condition A, an atomic layer deposition film under the following conditions, and a second chemical vapor deposition layer under the following condition A are placed on the surface of the PET film without an easy-adhesion layer. A barrier film was obtained by forming a film in this order.

(Parallel plate type plasma CVD device)
A plasma CVD apparatus (manufactured by Anerva, model number: PED-401) having a parallel plate type electrode structure was used for film formation of the first to third chemical vapor deposition layers. The distance between the upper electrode and the lower electrode was 28 mm. It is designed so that high-frequency power of 40 kHz is applied to the lower electrode having a diameter of 325 mm. The temperature of the lower electrode can be set by a chiller. The upper electrode is a shower head to introduce gas. A bubbler was installed to introduce the raw materials used for film formation, and the temperature could be set by a water bath. The gasified raw material is introduced into the plasma CVD apparatus from the bubbler via the needle valve. The pressure of the bubbler can be changed by adjusting the needle valve.

(Film deposition condition A of the first and second chemical vapor deposition layers (CVD-A))
The resin substrate was placed in the vacuum chamber of the plasma CVD apparatus and placed on the lower electrode. Further, in order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the resin film. The temperature of the lower electrode was 18 ° C. After closing the chamber and reducing the pressure to 1 Pa or less, Ar gas was used as a carrier gas, and the raw material HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus by bubbling. The flow rate of Ar gas was 3 sccm, the temperature of the bubbler was 30 ° C., and the pressure of the bubbler was 160 Torr. At this time, the flow rate of HMDSO was calculated to be 1.5 sccm. Separately, 50 sccm of oxygen gas was supplied, mixed with Ar gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 15 Pa, the discharge power was set to 100 W, and film formation was performed. The film formation time was 5 minutes. After the film formation time had elapsed, the discharge was stopped, the pressure was reduced to 1 Pa or less, and then venting was performed to return to atmospheric pressure.

(Conditions for forming an atomic layer deposition film (ALD))
An AlOx film was formed on the first chemical vapor deposition layer of the resin substrate by an atomic layer deposition method. At this time, TMA (trimethylaluminum) was used as the raw material gas, Ar was used as the purge gas, and oxygen was used as the reaction gas. The substrate was placed in a film forming apparatus for atomic layer deposition and installed on the stage. In order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the substrate. After installing the base material, the pressure was reduced to 1 Pa. For film formation, the introduction of each gas is switched, and 1. TMA 0.5 seconds, 2. Ar 4 seconds, 3. Oxygen 1 second, of which discharge 0.5 seconds, 4. 125 cycles were carried out with Ar 4 seconds as one cycle. The set temperature of the stage at the time of film formation is 80 ° C., the pressure at the time of film formation is 100 Pa, and the frequency of the power supply used is 13.56 MHz. After the film was formed, the pressure was reduced to 1 Pa, and then venting was performed and the mixture was returned to the atmosphere.

[Example 2]
(Film layer configuration: PET / CVD-D / CVD-A / ALD / CVD-A)
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 50 μm, with an easy-adhesion layer on one side) was prepared as a resin base material. A third chemical vapor deposition layer was formed on the surface of the PET film without an easy-adhesion layer under the following condition D. Subsequently, the first chemical vapor deposition layer, the atomic layer deposition film, and the second chemical vapor deposition layer were formed in this order under the same conditions as in Example 1 to obtain a barrier film.

(Film deposition condition D of the third chemical vapor deposition layer (CVD-D))
The substrate to be filmed was placed in the vacuum chamber of the plasma CVD apparatus and placed on the lower electrode.
Further, in order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the substrate. The temperature of the lower electrode was 18 ° C. After closing the chamber and reducing the pressure to 1 Pa or less, Ar gas was used as a carrier gas, and the raw material HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus by bubbling. The flow rate of Ar gas was 50 sccm, the temperature of the bubbler was 39 ° C., and the pressure of the bubbler was 160 Torr. At this time, the flow rate of HMDSO was calculated to be 51.5 sccm. Separately, 50 sccm of oxygen gas was supplied, mixed with Ar gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 20 Pa, the discharge power was set to 100 W, and film formation was performed. The film formation time was 30 seconds. After the film formation time had elapsed, the discharge was stopped, the pressure was reduced to 1 Pa or less, and then venting was performed to return to atmospheric pressure. Although the pressure is returned to atmospheric pressure for the convenience of film thickness measurement, the first chemical vapor deposition layer can be formed while the base material is still installed in the vacuum chamber.

[Example 3]
(Film layer configuration: PET / CVD-B / ALD / CVD-B)
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 50 μm, with an easy-adhesion layer on one side) was prepared as a resin base material. On the surface of the PET film without an easy-adhesion layer, the first chemical vapor deposition layer under the following condition B, the atomic layer deposition film under the condition of Example 1, and the second chemical vapor deposition under the following condition B. The layers were formed in this order to obtain a barrier film.

(Film deposition condition B of the first and second chemical vapor deposition layers (CVD-B))
The resin substrate was placed in the vacuum chamber of the plasma CVD apparatus and placed on the lower electrode. Further, in order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the resin film. The temperature of the lower electrode was 18 ° C. After closing the chamber and reducing the pressure to 1 Pa or less, Ar gas was used as a carrier gas, and the raw material HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus by bubbling. The flow rate of Ar gas was 3 sccm, the temperature of the bubbler was 30 ° C., and the pressure of the bubbler was 160 Torr. At this time, the flow rate of HMDSO was calculated to be 1.5 sccm. Separately, 50 sccm of oxygen gas was supplied, mixed with Ar gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 17 Pa, the discharge power was set to 100 W, and film formation was performed. The film formation time was 5 minutes. After the film formation time had elapsed, the discharge was stopped, the pressure was reduced to 1 Pa or less, and then venting was performed to return to atmospheric pressure.

[Example 4]
(Film layer configuration: PET / CVD-E / CVD-C / ALD / CVD-C)
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 50 μm, with an easy-adhesion layer on one side) was prepared as a resin base material. A third chemical vapor deposition layer was formed on the surface of the PET film without an easy-adhesion layer under the following condition E. Subsequently, the first chemical vapor deposition layer is formed under the following condition C, the atomic layer deposition film is formed under the condition of Example 1, and the second chemical vapor deposition layer is formed under the following condition C in this order to form a barrier. A sex film was obtained.

(Film deposition condition E of the third chemical vapor deposition layer (CVD-E))
The substrate to be filmed was placed in the vacuum chamber of the plasma CVD apparatus and placed on the lower electrode.
Further, in order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the substrate. The temperature of the lower electrode was 18 ° C. After closing the chamber and reducing the pressure to 1 Pa or less, Ar gas was used as a carrier gas, and the raw material HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus by bubbling. The flow rate of Ar gas was 50 sccm, the temperature of the bubbler was 39 ° C., and the pressure of the bubbler was 160 Torr. At this time, the flow rate of HMDSO was calculated to be 51.5 sccm. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 20 Pa, the discharge power was set to 100 W, and film formation was performed. The film formation time was 15 seconds. After the film formation time had elapsed, the discharge was stopped, the pressure was reduced to 1 Pa or less, and then venting was performed to return to atmospheric pressure.

(Film deposition condition C of the first and second chemical vapor deposition layers (CVD-C))
The resin substrate was placed in the vacuum chamber of the plasma CVD apparatus and placed on the lower electrode. Further, in order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the resin film. The temperature of the lower electrode was 18 ° C. After closing the chamber and reducing the pressure to 1 Pa or less, Ar gas was used as a carrier gas, and the raw material HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus by bubbling. The flow rate of Ar gas was 3 sccm, the temperature of the bubbler was 30 ° C., and the pressure of the bubbler was 160 Torr. At this time, the flow rate of HMDSO was calculated to be 1.5 sccm. Separately, 10 sccm of oxygen gas was supplied, mixed with Ar gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 15 Pa, the discharge power was set to 100 W, and film formation was performed. The film formation time was 5 minutes. After the film formation time had elapsed, the discharge was stopped, the pressure was reduced to 1 Pa or less, and then venting was performed to return to atmospheric pressure.

[Example 5]
(Film layer configuration: PET / CVD-F / CVD-B / ALD / CVD-A)
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 50 μm, with an easy-adhesion layer on one side) was prepared as a resin base material. A third chemical vapor deposition layer was formed on the surface of the PET film without an easy-adhesion layer under the following condition F. Subsequently, the first chemical vapor deposition layer is formed under the condition B of Example 2, the atomic layer deposition film is formed under the condition of Example 1, and the second chemical vapor deposition layer is formed under the condition A of Example 1. Then, a barrier film was obtained.

(Film deposition condition F of the third chemical vapor deposition layer (CVD-F))
The substrate to be filmed was placed in the vacuum chamber of the plasma CVD apparatus and placed on the lower electrode.
Further, in order to measure the film thickness, a silicon wafer whose surface was mirror-finished was partially masked and placed on a part of the substrate. The temperature of the lower electrode was 18 ° C. After closing the chamber and reducing the pressure to 1 Pa or less, Ar gas was used as a carrier gas, and the raw material HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus by bubbling. The flow rate of Ar gas was 50 sccm, the temperature of the bubbler was 39 ° C., and the pressure of the bubbler was 160 Torr. At this time, the flow rate of HMDSO was calculated to be 51.5 sccm. Separately, 50 sccm of oxygen gas was supplied, mixed with Ar gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 23 Pa, the discharge power was set to 20 W and the film was formed. The film formation time was 5 minutes. After the film formation time had elapsed, the discharge was stopped, the pressure was reduced to 1 Pa or less, and then venting was performed to return to atmospheric pressure.

[Comparative Example 1]
(Film layer composition: PEN / ALD)
A PEN film (manufactured by Teijin Limited, Q65HA, thickness 125 μm) was prepared as a resin base material. Only the atomic layer deposition film was formed on the surface of the PEN film having the easy-adhesion layer under the same conditions as in Example 1 to obtain a barrier film.

[Comparative Example 2]
(Film layer composition: PET / ALD)
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 50 μm, with an easy-adhesion layer on one side) was prepared as a resin base material. Only the atomic layer deposition film was formed on the surface of the PET film without the easy-adhesion layer under the same conditions as in Example 1 to obtain a barrier film.

<Performance evaluation of barrier film>
The following measurements were made on the barrier films produced in the above Examples and Comparative Examples.

(Measurement of barrier property)
Moisture vapor transmission rate (WVTR) was measured as the barrier property of the barrier film.
Samples having a WVTR of 0.1 g / m ² / day or more were measured using PERMATRAN-W 3/31 manufactured by MOCON under the conditions of 40 ° C. and 90% relative humidity.
Samples with a WVTR of less than 0.1 g / m ² / day were measured using DELTAPERM manufactured by Technolux under the conditions of 40 ° C. and 90% relative humidity in accordance with ISO 15106-5.

(Moisture resistance and heat resistance test)
The barrier property was measured after storing the barrier film at 85 ° C. and 85% RH for 120 hours.

(Weather resistance test)
Using a xenon weather meter (Xenon Weather-Ometer Ci5000 manufactured by ATLAS), the above barrier property was measured after performing an irradiation test for 120 hours from the barrier surface side under the conditions based on ISO 4892-2. rice field.

(Measurement of film thickness)
The film thickness of the barrier film is confirmed by measuring the step between the part where the chemical vapor deposition layer or the atomic layer deposition film is formed on the silicon wafer and the part where it does not exist with a surf coder ET4000L manufactured by Kosaka Research Institute. bottom.

(Measurement of optical characteristics)
The total light transmittance (Tt) was measured with a haze meter (HM-150 manufactured by Murakami Color Technology Laboratory) in accordance with JIS K7361.
Haze was measured with a haze meter (HM-150 manufactured by Murakami Color Technology Research Institute) in accordance with JIS K7136.

(Composition analysis)
The elemental composition was analyzed using an X-ray photoelectron spectroscopy analyzer (ESCA-3400 manufactured by KRATOS) under the conditions of an X-ray gun: MgKα, 20 mA, and 10 kV. The ion sputtering conditions for confirming the composition in the depth direction were 0.3 kV and 30 mA, and the elemental composition at each depth was analyzed by controlling the sputtering time.

The results of the above composition analysis were as follows.
-Composition of CVD-A Si: O: C = 33.4: 65.7: 0.9
・ Composition of CVD-B Si: O: C = 33.3: 65.6: 1.1
・ Composition of CVD-C Si: O: C = 32.4: 60.7: 6.9
・ Composition of CVD-D Si: O: C = 30.2: 47.0: 22.8
-Composition of CVD-E Si: O: C = 28.6: 40.3: 31.1
・ Composition of CVD-F Si: O: C = 32.4: 43.1: 24.5
・ Composition of ALD Al: O: C = 36.5: 60.1: 3.4
In the first to third chemical vapor deposition layers, the ratio of nitrogen was 0.4% with respect to the total of 100% of the four elements of silicon, oxygen, carbon, and nitrogen.
Further, in the atomic layer deposition film, the ratio of nitrogen was 0.5% with respect to the total of 100% of the four elements of aluminum, oxygen, carbon, and nitrogen.

The results of each of the above measurements are summarized in Table 1.

10, 20 Barrier film 11 Resin base material 12 First chemical vapor deposition layer 13 Atomic layer deposition film 14 Second chemical vapor deposition layer 15 Third chemical vapor deposition layer

Claims (8)

A barrier film comprising a resin base material, a first chemical vapor deposition layer, an atomic layer deposition film, and a second chemical vapor deposition layer in this order.
The first chemical vapor deposition layer contains silicon, oxygen and carbon.
The atomic layer deposition film contains aluminum and oxygen and contains
The second chemical vapor deposition layer contains silicon, oxygen and carbon and contains
In the first chemical vapor deposition layer and the second chemical vapor deposition layer, the ratio of carbon to 100% of the total of the three elements of silicon, oxygen, and carbon is 0.1% or more and less than 15%. can be,
A third chemical vapor deposition layer is further provided between the resin substrate and the first chemical vapor deposition layer, and the third chemical vapor deposition layer contains silicon, oxygen and carbon, and is silicon. A barrier film having a carbon content of 15% or more and 40% or less with respect to a total of 100% of the three elements of, oxygen, and carbon. The first chemical vapor deposition layer and the second chemical vapor deposition layer further contain nitrogen, and the ratio of nitrogen to 100% of the total of the four elements of silicon, oxygen, carbon, and nitrogen is 1%. The barrier film according to claim 1, which is as follows. The barrier according to claim 1 or 2, wherein the barrier film has an easy-adhesion layer on the resin base material, and the first chemical vapor deposition layer is not directly provided on the easy-adhesion layer. Sex film. The barrier film according to any one of claims 1 to 3, wherein a layer containing a lubricant is not provided on at least one surface of the resin base material. The barrier film according to any one of claims 1 to 4, wherein the water vapor transmittance is 1.0 × ^10-2 g / m ^{2 / day or less.} The barrier film according to any one of claims 1 to 5, wherein the total light transmittance is 85% or more. The barrier film according to any one of claims 1 to 6, wherein the water vapor transmittance after storage at 85 ° C. and 85% RH for 120 hours is 1 g / m ^{2 / day or less.} The barrier according to any one of claims 1 to 7, wherein the water vapor permeability after an irradiation test for 120 hours with a xenon weather meter is 1 g / m ^{2 / day or less in accordance with ISO 4892-2.} Sex film.

Images