JP6988978B2 - Barrier film - Google Patents

Description

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

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 vapor 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, the barrier film laminated with aluminum foil or the like is excellent in gas blocking property, but is opaque. Therefore, in order to avoid accidents due to misidentification of the contents, visibility of the contents for pharmaceuticals and the like is required. It cannot be used in applications.

In response to the above technical problems, a first layer formed of a plastic material and a polymer of an organosilicon compound containing at least silicon, oxygen, and carbon provided on the plastic material, and a first layer provided on the first layer. A gas-blocking laminated plastic material composed of a second layer of silicon oxide has been proposed (see Patent Document 1). Since the plastic material described in Patent Document 1 has a water vapor permeability of about 0.2 to 0.4 g / m ² / day, a barrier film having further excellent water vapor barrier properties is still desired.

Japanese Unexamined Patent Publication No. 5-345383

The present invention has been made in view of the above background art, and an object thereof is 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. To do.

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 was found that by forming a layer, 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. 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, and a second chemical vapor deposition layer in this order.
_{The first chemical vapor deposition layer contains silicon, oxygen, and carbon, and the ratio C 1 of} carbon is 15% or more and 25 % or less with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. can be,
_{The second chemical vapor deposition layer contains silicon, oxygen, and carbon, and the ratio C 2 of} carbon is 1% or more and 20% or less with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. can be,
_{The ratio C 1} of carbon in the _{first chemical vapor deposition layer and the ratio C 2} of carbon in the second chemical vapor deposition layer satisfy C ₁ > C _2.
A barrier film having a water vapor transmission rate of 5.0 × 10 ⁻² g / m ² / day or less is provided.
In the aspect of the present invention, the barrier film preferably has a total light transmittance of 80% or more.
In embodiments of the present invention, the barrier film ^is preferably ^{b *} is 2 or less in the L ^* a * ^{b *} display system.
^{In the embodiment of the present invention, the barrier film has a water vapor transmission rate of 5.0 × 10 −2} 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%. Is preferable.
In embodiments of the present invention, the first thickness of the chemical vapor deposition layer T ₁ and the second chemical vapor deposition layer thickness T _2, it is preferable to satisfy T 1 _{<T 2.}
In the aspect of the present invention, _{it is preferable that the thickness T 1 of} the first chemical vapor deposition layer is 10 nm or more and less than 50 nm.
In the aspect of the present invention, the thickness T _{2 of} the second chemical vapor deposition layer is preferably 50 nm or more and 500 nm or less.
In the aspect of the present invention, it is preferable that the surface roughness Ra of the resin base material on the first chemical vapor deposition layer side is 5 nm or less.
In the aspect of the present invention, the barrier film further includes a flattening layer between the resin base material and the first chemical vapor deposition layer, and the first chemical vapor deposition layer side of the barrier film. The surface roughness Ra of the flattening layer is preferably 5 nm or less.
In the aspect of the present invention, the barrier film is for a packaging material.
In the aspect of the present invention, a packaged product containing the barrier film is provided.
In the aspect of the present invention, an electric / electronic product including the barrier film is provided.

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. Such a barrier film can be suitably used for medical packaging materials and the like that 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 phase vapor deposition layer, and a second chemical vapor phase vapor deposition layer in this order. The barrier film may further include a flattening 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 5.0 × 10 ^-2 g / m ² / day or less, preferably 3.0 × 10 ^-2 g / m ² / day or less. Yes, more preferably 1.0 × 10 ^-2 g / m ² / day or less, still more preferably 5.0 × 10 ^-3 g / m ² / day or less, and even more preferably 1.0 × 10 ^{−. It is 3} 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 that require a high degree of water vapor barrier property. The temperature of the water vapor transmission rate is based on JIS K7129B using a water vapor transmission rate measuring machine (MOCON: PERMATRAN) or ISO 15106-5 using Tecnolox DELTA PARM. It can be measured in an environment of 40 ° C. and 90% humidity.

^{The barrier film has a water vapor transmission rate of preferably 5.0 × 10-2} 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%, more preferably 3. It is 0 × 10 ^-2 g / m ² / day or less, more preferably 1.0 × 10 ^-2 g / m ² / day or less, and even more preferably 5.0 × 10 ^-3 g / m ² / day. It is as follows. 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 transparency, and the total light transmittance is preferably 80% or more, more preferably 85% 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 according to JIS K7361 using HAZE METER HM-150 manufactured by Murakami Daylighting Research Institute Co., Ltd.

The barrier film has excellent permeability and a haze of preferably 5% or less, more preferably 3% or less, and further 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.

Barrier film, color is colorless and transparent, L ^* a ^* b ^* is b ^* is preferably in the display system is 3 or less, more preferably 2 or less, more preferably 1.5 or less. L ^* a ^* b ^* satisfies the b ^* is the value range of the display system, excellent visibility of the contents when used as a packaging material. ^{Incidentally, b *} in the L ^* a * ^{b *} display system, using a JASCO Corp. ultraviolet-visible-near-infrared spectrophotometer V-7100, can be measured in accordance with JIS Z8701-1999.

The layer structure of the barrier film will be described with reference to the drawings. The barrier film 10 shown in FIG. 1 includes a resin base material 11, a first chemical vapor deposition layer 12, and a second chemical vapor deposition layer 13 in this order. Further, the barrier film 20 shown in FIG. 2 includes a resin base material 11, a flattening layer 14, a first chemical vapor deposition layer 12, and a second chemical vapor deposition layer 13 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 polyamide, are preferable. The resin base material made of these thermoplastic resins may be a single layer or a laminated body 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 layer, 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.

The surface roughness Ra of the resin base material on the side in contact with the first chemical vapor deposition layer is preferably 5 nm or less, more preferably 3 nm or less, and further preferably 2 nm or less. If the surface roughness Ra of the resin base material on the side in contact with the first chemical vapor phase vapor deposition layer satisfies the above values, the adhesion to the first chemical vapor phase vapor deposition layer is improved, and the water vapor barrier property, particularly high temperature and high temperature, is high. Excellent water vapor barrier even after storage in a humid environment.

<Chemical vapor deposition layer>
The thin-film vapor deposition layer constituting the barrier film according to the present invention is a thin-film deposition film formed by a chemical vapor deposition method (CVD method). The barrier film includes a first chemical vapor deposition layer and a second chemical vapor deposition layer in this order from the resin substrate side. 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 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.

_{The first chemical vapor deposition layer has a carbon ratio C 1} of 15% or more and 40% or less, preferably 16% or more and 30% with respect to a total of 100% of the three elements of silicon, oxygen, and carbon. It is less than or equal to 17.5% or more and more preferably 25% or less.
_{The second chemical vapor deposition layer has a carbon ratio C 2} of 1% or more and 20% or less, preferably 5% or more and 15% with respect to a total of 100% of the three elements of silicon, oxygen, and carbon. It is less than or equal to 7.5% or more, and more preferably 12.5% or less.
Further, the carbon ratio C ₁ in the first chemical vapor deposition layer and the carbon ratio C _{2 in} the second chemical vapor deposition layer satisfy C ₁ > C _{2.
When the ratio C 1} of carbon in the first chemical gas phase vapor deposition layer C _{1 and the ratio C 2} of carbon in the second chemical gas phase vapor deposition layer satisfy the above conditions, the heat elongation of the resin base material during the heat treatment can be obtained. The followability is improved, and the water vapor barrier property is excellent even after storage in a high temperature and high humidity environment.

It is preferable that the thickness T ₁ of the first chemical vapor deposition layer and the thickness T ₂ of the second chemical vapor deposition layer satisfy _{T 1} <T _{2.
Further, the thickness T 1} of the first chemical vapor deposition layer is preferably 10 nm or more and less than 50 nm, more preferably 11 nm or more and 30 nm or less, and further preferably 15 nm or more and 25 nm or less.
_{The thickness T 2} of the second chemical vapor deposition layer is preferably 50 nm or more and 500 nm or less, more preferably 75 nm or more and 400 nm or less, and further preferably 100 nm or more and 300 nm or less.
The thickness T ₂ of the first chemical thickness of vapor deposition layer T ₁ and the second chemical vapor deposition layer that satisfies the above conditions, the barrier film is after storage under high temperature and high humidity environments Even if it exists, it has excellent water vapor barrier properties. The thickness of the chemical vapor deposition layer can be adjusted to a desired range by adjusting the film transport speed during vapor deposition by the CVD method.

<Flatration layer>
The barrier film may further include a flattening layer between the resin substrate and the first chemical vapor deposition layer. The surface roughness Ra on the side of the flattening layer in contact with the first chemical vapor deposition layer is preferably 5 nm or less, more preferably 3 nm or less, still more preferably 2 nm or less, and even more preferably. It is 1 nm or less. If the surface roughness Ra of the flattening layer on the side in contact with the first chemical vapor deposition layer satisfies the above values, the adhesion to the first chemical vapor deposition layer is improved, and the water vapor barrier property, particularly high temperature and high temperature, is high. Excellent water vapor barrier even after storage in a humid environment.

The composition of the flattening layer is not particularly limited as long as the surface roughness Ra satisfies the above numerical values. In order to improve visibility when used as a packaging material, it is preferable to use a highly transparent material. For example, a resin material such as the above-mentioned thermosetting resin or thermoplastic resin used as a material for a resin base material can be used.

<Manufacturing method of barrier film>
In the method for producing a barrier film according to the present invention, a film-forming monomer gas containing at least one organic silicon compound is used as a raw material on a resin base material, and an inert gas such as argon gas or helium gas is used as a carrier gas. First and second chemical vapor deposition containing silicon oxide using a plasma chemical vapor deposition method that uses oxygen gas or the like as the oxygen supply gas and uses a plasma generator or the like. Layers can be formed.

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 mixed gas composition for film formation, for example, a monomer gas for film formation:
A mixed gas composition for film formation or the like having a gas composition ratio of oxygen gas: inert gas = 1: 0 to 20:00 to 5 (unit: slm, abbreviation for standard liter minute) can be used.
By using such a mixed gas composition for film formation, silicon oxide is mainly used, and at least one compound composed of one or more elements of carbon, hydrogen, silicon or oxygen is chemically bonded to the silicon oxide. It is possible to form a vapor-deposited film contained therein. By adjusting the mixing ratio of each gas component of the mixed gas composition for film formation, the ratios of silicon, oxygen, and carbon contained in the first and second chemical gas phase 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 viewpoint 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.

<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, solar cells, organic light emitting diodes, and electric / electronic products such as display devices.

<Packaging material>
The barrier film according to the present invention can be particularly preferably 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 particularly preferably used as a packaging material for pharmaceuticals.

<Other aspects>
Another object of the present invention is 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.

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 was found that by forming a layer, 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. 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, and a second chemical vapor deposition layer in this order.
_{The first chemical vapor deposition layer contains silicon, oxygen, and carbon, and the ratio C 1 of} carbon is 15% or more and 40% or less with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. can be,
_{The second chemical vapor deposition layer contains silicon, oxygen, and carbon, and the ratio C 2 of} carbon is 1% or more and 20% or less with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. can be,
_{The ratio C 1} of carbon in the _{first chemical vapor deposition layer and the ratio C 2} of carbon in the second chemical vapor deposition layer satisfy C ₁ > C _2.
A barrier film having a water vapor transmission rate of 5.0 × 10 ⁻² g / m ² / day or less is provided.
In another aspect of the present invention, the barrier film preferably has a total light transmittance of 80% or more.
In another aspect of the present invention, the barrier film is preferably b ^* is 2 or less in the L ^* a ^* b ^* display system.
^{In another aspect of the present invention, the barrier film has a water vapor transmission rate of 5.0 × 10 −2} 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%. Is preferable.
In another aspect of the present invention, the first thickness of the chemical vapor deposition layer T ₁ and the second chemical vapor deposition layer thickness T _2, it is preferable to satisfy T 1 _{<T 2} ..
In another aspect of the present invention, _{it is preferable that the thickness T 1 of} the first chemical vapor deposition layer is 10 nm or more and less than 50 nm.
In another aspect of the present invention, the thickness T _{2 of} the second chemical vapor deposition layer is preferably 50 nm or more and 500 nm or less.
In another aspect of the present invention, the surface roughness Ra of the resin base material on the first chemical vapor deposition layer side is preferably 5 nm or less.
In another aspect of the present invention, the barrier film further comprises a flattening layer between the resin substrate and the first chemical vapor deposition layer, and the first chemical vapor deposition layer side. The surface roughness Ra of the flattening layer is preferably 5 nm or less.

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. Such a barrier film can be suitably used for medical packaging materials and the like that require visibility.

<Manufacturing of barrier film>
[Example 1]
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4100, thickness 100 μm, surface roughness Ra 1.2 nm) was prepared as a resin base material. A first chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 30:52:18 was formed on one surface of the PET film using a plasma CVD apparatus under the following conditions.
(Evaporation condition 1 of the first chemical vapor deposition layer)
・ Input power 0.3kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 5Pa
・ Film thickness 22 nm
・ Film transfer speed 2m / min

Subsequently, on the first chemical vapor deposition layer, a second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 31:59:10 under the following conditions using a plasma CVD apparatus is used. Was formed to obtain a barrier film.
(Evaporation condition 1 of the second chemical vapor deposition layer)
・ Input power 0.7kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 3.5Pa
・ Film thickness 110nm
・ Film transfer speed 0.5m / min

[Comparative Example 1]
A barrier film was obtained in the same manner as in Example 1 except that the second chemical vapor deposition layer was directly formed on the PET film without forming the first chemical vapor deposition layer.

[Comparative Example 2]
A barrier film was obtained in the same manner as in Example 1 except that the second chemical vapor deposition layer was not formed.

[Comparative Example 3]
A barrier film was obtained in the same manner as in Example 1 except that the first chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 25:30:45 was formed under the following conditions.
(Evaporation condition 2 of the first chemical vapor deposition layer)
・ Input power 0.3kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/0 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 5Pa
・ Film thickness 22 nm
・ Film transfer speed 2m / min

[Comparative Example 4]
A barrier film was obtained in the same manner as in Example 1 except that a biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4300, thickness 100 μm, surface roughness Ra 6.5 nm) was used as the resin base material.

[Example 2]
A biaxially stretched PET film (manufactured by Toyobo Co., Ltd .: A4300, thickness 100 μm, surface roughness Ra 6.5 nm) was prepared as a resin base material. A flattening layer (main component acrylic resin, surface roughness Ra 0.8 nm) was provided on one surface of the PET film. Next, a first chemical vapor deposition vapor deposition layer was formed on the flattening layer in the same manner as in Example 1 using a plasma CVD apparatus.

Subsequently, a second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 31:59:10 is formed on the first chemical vapor deposition layer under the following conditions to provide a barrier property. I got a film.
(Evaporation condition 2 of the second chemical vapor deposition layer)
・ Input power 0.7kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 3.5Pa
・ Film thickness 59 nm
・ Film transfer speed 1.0m / min

[Example 3]
Same as Example 2 except that the second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 31:59:10 was formed under the vapor deposition condition 1 of the second chemical vapor deposition layer. A barrier film was obtained.

[Example 4]
A barrier film was obtained in the same manner as in Example 2 except that a second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 31:59:10 was formed under the following conditions.
(Evaporation condition 3 of the second chemical vapor deposition layer)
・ Input power 0.7kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 3.5Pa
-Film thickness 232 nm
・ Film transfer speed 0.2m / min

[Example 5]
A barrier film was obtained in the same manner as in Example 2 except that a second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 31:59:10 was formed under the following conditions.
(Evaporation condition 4 of the second chemical vapor deposition layer)
・ Input power 0.7kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 3.5Pa
・ Film thickness 422 nm
・ Film transfer speed 0.1 m / min

[Example 6]
A barrier film was obtained in the same manner as in Example 2 except that the first chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 30:52:18 was formed under the following conditions.
(Evaporation condition 3 of the first chemical vapor deposition layer)
・ Input power 0.3kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 5Pa
・ Film thickness 11 nm
・ Film transfer speed 4m / min

[Example 7]
A barrier film was obtained in the same manner as in Example 2 except that the first chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 30:49:21 was formed under the following conditions.
(Evaporation condition 4 of the first chemical vapor deposition layer)
・ Input power 0.3kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 200/200/1500 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 5Pa
・ Film thickness 22 nm
・ Film transfer speed 2m / min

[Example 8]
A barrier film was obtained in the same manner as in Example 2 except that a second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 57: 31: 12 was formed under the following conditions.
(Evaporation condition 5 of the second chemical vapor deposition layer)
・ Input power 0.7kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/900 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 3.5Pa
・ Film thickness 110nm
・ Film transfer speed 0.5m / min

[Comparative Example 5]
A barrier film was obtained in the same manner as in Example 2 except that a second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 29:47:24 was formed under the following conditions.
(Evaporation condition 6 of the second chemical vapor deposition layer)
・ Input power 0.7kW
・ Raw material gas composition HMDSO
・ He / Mn / O ₂ 100/100/150 sccm
・ Ar 100sccm for electrodes
・ Film formation pressure 3.5Pa
・ Film thickness 110nm
・ Film transfer speed 0.5m / min

[Comparative Example 6]
A barrier film was obtained in the same manner as in Example 2 except that the second chemical vapor deposition layer was directly formed on the flattening layer without forming the first chemical vapor deposition layer.

[Comparative Example 7]
A barrier film was obtained in the same manner as in Example 2 except that the second chemical vapor deposition layer was not formed.

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

(Measurement of water vapor transmission rate)
The water vapor transmission rate of the barrier film is based on JIS K7129B using a water vapor transmission rate measuring machine (MOCON: PERMATRAN) or ISO 15106-5 using Teknolox DELTA PARM. Then, the measurement was carried out in an environment of a temperature of 40 ° C. and a humidity of 90%. Further, after storing the barrier film in an environment of a temperature of 85 ° C. and a humidity of 85% for 120 hours, the water vapor transmission rate was measured in the same manner. The measurement results are as shown in Table 1 below.

(Measurement of total light transmittance)
The total light transmittance of the barrier film was measured using HAZE METER HM-150 manufactured by Murakami Daylighting Laboratory Co., Ltd. in accordance with JIS K7361. The measurement results are as shown in Table 1 below.

(Measurement of haze)
The haze of the barrier film was measured using HAZE METER HM-150 manufactured by Murakami Daylighting Laboratory Co., Ltd. in accordance with JIS K7136. The measurement results are as shown in Table 1 below.

(Measurement of chromaticity)
The ^{b *} in ^{the L} * ^a * ^{b *} display system of barrier film, using a JASCO Corp. ultraviolet-visible-near-infrared spectrophotometer V-7100, was measured in accordance with JIS Z8701-1999. The measurement results are as shown in Table 1 below.

Explanation of the sign

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

Claims (12)

A barrier film comprising a resin base material, a first chemical vapor deposition layer, and a second chemical vapor deposition layer in this order.
_{The first chemical vapor deposition layer contains silicon, oxygen, and carbon, and the ratio C 1 of} carbon is 15% or more and 25 % or less with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. can be,
_{The second chemical vapor deposition layer contains silicon, oxygen, and carbon, and the ratio C 2 of} carbon is 1% or more and 20% or less with respect to the total of 100% of the three elements of silicon, oxygen, and carbon. can be,
_{The ratio C 1} of carbon in the _{first chemical vapor deposition layer and the ratio C 2} of carbon in the second chemical vapor deposition layer satisfy C ₁ > C _2.
A barrier film having a water vapor transmission rate of 5.0 × 10 ⁻² g / m ² / day or less. The barrier film according to claim 1, wherein the total light transmittance is 80% or more. L ^* a ^* b ^* B in the display system ^* The barrier film according to claim 1 or 2, wherein is 3 or less. The water vapor transmission rate after storage for 120 hours in an environment with a temperature of 85 ° C and a humidity of 85% is 5.0 × 10. ^-2 g / m ² The barrier film according to any one of claims 1 to 3, which is less than or equal to / day. Thickness T of the first chemical vapor deposition layer ₁ And the thickness T of the second chemical vapor deposition layer ₂ But T ₁ <T ₂ The barrier film according to any one of claims 1 to 4, which satisfies the above conditions. Thickness T of the first chemical vapor deposition layer ₁ The barrier film according to any one of claims 1 to 5, wherein the film is 10 nm or more and less than 50 nm. Thickness T of the second chemical vapor deposition layer ₂ The barrier film according to any one of claims 1 to 6, wherein the film is 50 nm or more and 500 nm or less. The barrier film according to any one of claims 1 to 7, wherein the surface roughness Ra of the resin base material on the first chemical vapor deposition layer side is 5 nm or less. The barrier film further includes a flattening layer between the resin base material and the first chemical vapor deposition layer, and the surface roughness of the flattening layer on the side of the first chemical vapor deposition layer. The barrier film according to any one of claims 1 to 8, wherein Ra is 5 nm or less. The barrier film according to any one of claims 1 to 9, which is used as a packaging material. A packaged product comprising the barrier film according to any one of claims 1 to 9. An electrical / electronic product comprising the barrier film according to any one of claims 1 to 9.

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