JP6846008B2 - Barrier film manufacturing method - Google Patents

Description

The present invention relates to a method for producing a barrier film, and more particularly, to produce a barrier film comprising a resin base material, a first chemical vapor deposition layer, and a second chemical vapor deposition layer in this order. Regarding the method.

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

Applications of the barrier film include base materials used for panels such as solar cells, organic EL displays, organic EL lighting, liquid crystal displays, and electronic paper. Further, as a material for a backlight of a liquid crystal display, a quantum dot material having a problem in moisture and heat resistance may be used, and a base material for protecting the quantum dot material is also required to have a barrier property. These substrates are required to have durability such as weather resistance and moisture heat resistance as well as barrier property and transparency.

In response to the above technical issues such as barrier property and transparency, 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. A gas-blocking laminated plastics material composed of a second layer of silicon oxide provided on the layer has been proposed (see Patent Document 1). Further, after forming a reinforced adhesion layer containing a region having a carbon concentration of 25 to 30 element% on a substrate by a plasma CVD method based on the three elements of silicon, oxygen, and carbon, a barrier layer having a carbon concentration of 5 element% or less is formed. Further formed vapor deposition film has been proposed (see Patent Document 2).

Japanese Unexamined Patent Publication No. 5-345383 Japanese Unexamined Patent Publication No. 2005-97678

The weather resistance of the plastic materials described in Patent Document 1 and the vapor-deposited film described in Patent Document 2 has not been sufficiently studied, and a new technique that the barrier performance at the time of film formation deteriorates after the weather resistance test. I found a problem. Further, in the examples of Patent Document 2, although only HMDSO having a large proportion of C element in the molecule is used, the C concentration in the adhesion layer is 30 element% or less, so that the decomposition has progressed to some extent. It is inferred that. This indicates that the output of the discharge is large with respect to the processing conditions such as the amount of gas, the film forming pressure, and the electrode size. That is, the intensity of the plasma is strong, and the resin base material is damaged. Furthermore, since the thickness of the adhesion layer described in the examples is several nm or less, the obtained thin film is considered to have an island-like structure and does not completely cover the surface of the resin, so that it is a barrier. There is a technical problem that the base material is damaged during layer formation.

The present invention has been made in view of the above background art, and an object of the present invention is to provide a method for producing a barrier film having excellent transparency and excellent water vapor barrier property even after a weather resistance test. It is in.

As a result of diligent studies to solve the above problems, the present inventors have formed a first chemical vapor deposition layer on a resin substrate by a chemical vapor deposition method (CVD method). It was found that by adjusting the parameters of the film conditions, it is possible to provide a barrier film having excellent transparency and excellent water vapor barrier property even after the weather resistance test. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention.
A method for producing a barrier film, which comprises 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 is expressed by the following formula:
E ₁ = W ÷ (S × P × F)
0.05 ≤ E ₁ ≤ 1.20
(In the formula, E ₁ is the plasma intensity, W is the electric power (W) at the time of film formation, S is the electrode area (m ² ) of the film forming apparatus or the area of the discharge part (m ² ), and P. Is the pressure (Pa) at the time of film formation, and F is the total flow rate (sccm) of the gas used at the time of film formation.)
A method is provided, which comprises forming a film under the film forming conditions satisfying the above conditions.

In the embodiment of the present invention, the second chemical vapor deposition layer is formed by the following formula:
E ₂ = W ÷ (S × P × F)
E ₁ <E ₂
1.00 ≤ E ₂ ≤ 3.00
(In the formula, E ₂ is the plasma intensity, W is the electric power (W) at the time of film formation, S is the electrode area (m ² ) of the film forming apparatus or the area of the discharge part (m ² ), and P. Is the pressure (Pa) at the time of film formation, and F is the total flow rate (sccm) of the supplied gas at the time of film formation.)
It is preferable to form a film under the film forming conditions satisfying the above conditions.

In the aspect of the present invention, the thickness T _{1 of} the first chemical vapor deposition layer is preferably 10 nm or more and 1000 nm or less.

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 1000 nm or less.

A barrier coat layer obtained by hydrolyzing and polycondensing a barrier coat solution containing at least one alkoxide and one water-soluble polymer may be provided on the second chemical vapor deposition layer.

In the aspect of the present invention, the total light transmittance of the barrier film is preferably 80% or more.

In the aspect of the present invention, the haze of the barrier film is preferably 10% or less.

According to the present invention, it is possible to provide a method for producing a barrier film having excellent transparency and excellent water vapor barrier property even after a weather resistance test. The barrier film obtained by the production method of the present invention can be suitably used for medical packaging materials, display panels, and the like, which require visibility.

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

<Manufacturing method of barrier film>
The present invention relates to a method for producing a barrier film including a resin base material, a first chemical vapor deposition layer, and a second chemical vapor deposition layer in this order. More specifically, a film-forming monomer gas containing one or more organic silicon compounds is used as a raw material on a resin substrate, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is further provided. It is possible to form the first and second chemical vapor deposition layers containing silicon oxide by using a plasma chemical vapor deposition method using an oxygen gas or the like as a supply gas and using a plasma generator or the like. it can.

In the production method of the present invention, the first chemical vapor deposition layer is formed by the following formula:
E ₁ = W ÷ (S × P × F)
0.05 ≤ E ₁ ≤ 1.20
(In the formula, E ₁ is the plasma intensity, W is the electric power (W) at the time of film formation, S is the electrode area (m ² ) of the film forming apparatus or the area of the discharge part (m ² ), and P. Is the pressure (Pa) at the time of film formation, and F is the total flow rate (sccm) of the gas used at the time of film formation.)
It is characterized in that the film is formed under the film forming conditions satisfying. The total flow rate of the gas used during film formation refers to the total flow rate of the above-mentioned monomer gas for film formation, carrier gas (inert gas), and oxygen supply gas. Furthermore, the above film formation conditions are
0.10 ≤ E ₁ ≤ 1.00
It is preferable to meet
0.20 ≤ E ₁ ≤ 0.80
It is more preferable to satisfy.
When the plasma intensity E ₁ is within the above numerical range, the plasma intensity is appropriate. Therefore, even if the vapor-deposited film is directly formed on the resin base material, the damage to the resin base material due to plasma is suppressed and the weather resistance is improved. be able to. In the present invention, a resin base material in which a layer such as an easy-adhesion layer is previously provided on the base material may be used, and even in such a case, a thin-film deposition film is directly formed on the resin base material. Corresponds to.

In the production method of the present invention, the second chemical vapor deposition layer is formed by the following formula:
E ₂ = W ÷ (S × P × F)
E ₁ <E ₂
1.00 ≤ E ₂ ≤ 3.00
(In the formula, E ₂ is the plasma intensity, W is the electric power (W) at the time of film formation, S is the electrode area (m ² ) of the film forming apparatus or the area of the discharge part (m ² ), and P. Is the pressure (Pa) at the time of film formation, and F is the total flow rate (sccm) of the gas used at the time of film formation.)
It is preferable to form a film under the film forming conditions satisfying the above conditions. Furthermore, the above film formation conditions are
1.10 ≤ E ₂ ≤ 2.50
More preferably
1.20 ≤ E ₂ ≤ 2.00
It is more preferable to satisfy.
Since the second chemical vapor deposition layer is formed on the first chemical vapor deposition layer, even if the plasma intensity E ₂ is higher than the plasma intensity E ₁ , the plasma at the time of the second chemical vapor deposition film formation There is almost no damage to the resin base material. By satisfying the above numerical range, the plasma intensity E ₂ can form a dense film having a higher barrier property.

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. For example, it is preferable to use a parallel plate type plasma CVD apparatus or a roll-to-roll type plasma CVD apparatus.

When a parallel plate type plasma CVD apparatus (manufactured by Anerva, model number: PED-401) is used, for example, the distance between the upper electrode and the lower electrode is 28 mm. High frequency power of 40 kHz can be introduced into the lower electrode having a diameter of 325 mm. In addition, the temperature of the lower electrode can be set by a chiller. The upper electrode is a shower head to introduce gas. A bubbler for introducing the raw material used for film formation is installed outside the plasma CVD apparatus, and the temperature can 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.

When a roll-to-roll type plasma CVD apparatus is used, for example, an apparatus capable of forming a film on a long resin base material and having a main roll for film formation having a diameter of 400 mm and a width of 350 mm is used. The discharge portion (mask opening) is 170 mm in the flow direction and 275 mm in the width direction. A magnet such as that used in a sputtering device is arranged in the discharge section at a distance of 70 mm from the main roll. Further, a T-shaped pipe for introducing gas is provided in the vicinity of the discharge portion, and gas is supplied from a large number of holes provided in the head portion of the T-shape. A bubbler for introducing the raw material used for film formation is installed outside the plasma CVD apparatus, and the temperature can 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. High frequency power of 40 kHz can be introduced into the main roll.

The mixing ratio of each gas component of the mixed gas composition for film formation is, for example, a gas composition of monomer gas for film formation: oxygen supply gas: inert gas = 1: 0 to 100: 0 to 100 (unit: sccm). A mixed gas composition for film formation consisting of a ratio can be used. By using such a mixed gas composition for film formation, a vapor-deposited film containing elements such as silicon, oxygen, and carbon can be formed. 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 and second 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 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.

<Barrier film>
The barrier film obtained by the method of the present invention comprises a resin base material, a first chemical vapor deposition layer, and a second chemical vapor deposition layer in this order, and is excellent in transparency and has excellent transparency. Excellent water vapor barrier property even after weather resistance test.

The barrier film has excellent water vapor barrier properties and has a water vapor permeability of preferably 9.0 × 10 ^-1 g / m ² / day or less, more preferably 1.0 × 10 ^-1 g / m ² / day. It is less than or equal to day, more preferably 5.0 × 10 ^-2 g / m ² / day or less, and even more preferably 1.0 × 10 ^-2 g / m ² / day or less. If the water vapor permeability satisfies the above numerical range, it can be used as a packaging material or a base material even in applications requiring a high degree of water vapor barrier property. The temperature of the water vapor permeability is determined by using a water vapor permeability measuring machine (MOCON: PERMATRAN), JIS K7129B, or Teknolux DELTAPERM, and ISO 15106-5. It can be measured in an environment of 40 ° C. and 90% humidity.

The water vapor permeability of the barrier film after the weather resistance test (120 hours) is preferably 9.0 × 10 ^-1 g / m ² / day or less, and more preferably 1.0 × 10 ^-1 g / day. It is m ² / day or less, more preferably 5.0 × 10 ^-2 g / m ² / day or less, and even more preferably 1.0 × 10 ^-2 g / m ² / day or less. If the water vapor transmittance after the weather resistance test satisfies the above numerical range, it is possible to suppress peeling of the vapor-deposited layer or deterioration of adhesion due to light, and it can be suitably used as a packaging material or a base material. The weather resistance test can be carried out under conditions compliant with ISO 4892-2.

The barrier film has excellent light transmittance, 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 in accordance with JIS K7361 using HAZE METER HM-150 manufactured by Murakami Color Research Institute Co., Ltd.

The barrier film is excellent in permeability and has a haze of preferably 10% or less, more preferably 5% or less, still more preferably 3% 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 Color 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 includes a resin base material 11, 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 obtained by the method of 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 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.

<Chemical vapor deposition layer>
The thin-film deposition layer constituting the barrier film obtained by the method of 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 base material 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.

In the first chemical vapor deposition layer, the ratio of silicon to 100% of the total of the three elements of silicon, oxygen, and carbon is preferably 25% or more and 40% or less, and more preferably 28% or more and 35. % Or less, the oxygen ratio is preferably 35% or more and 70% or less, more preferably 40% or more and 66% or less, and the carbon ratio is preferably 1% or more and 35% or less. It is preferably 10% or more and 32% or less.

In the second chemical vapor deposition layer, the ratio of silicon to 100% of the total of the three elements of silicon, oxygen, and carbon is preferably 25% or more and 40% or less, and more preferably 28% or more and 35. % Or less, the oxygen ratio is preferably 50% or more and 70% or less, more preferably 60% or more and 67% or less, and the carbon ratio is preferably 0.1% or more and 20% or less. , More preferably 0.1% or more and 10% or less.

_{The thickness T 1} of the first chemical vapor deposition layer is preferably 10 nm or more and less than 1000 nm, more preferably 15 nm or more and 800 nm or less, and further preferably 20 nm or more and 500 nm or less.
_{The thickness T 2} of the second chemical vapor deposition layer is preferably 50 nm or more and 1000 nm or less, more preferably 100 nm or more and 600 nm or less, and further preferably 150 nm or more and 500 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 a post-storage after the weather resistance test Also 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 formation time or film transport speed during vapor deposition by the CVD method.

<Barrier coat layer>
The barrier film obtained by the method of the present invention may further include a barrier coat layer on the second chemical vapor deposition layer. The barrier coat layer is a layer having a gas barrier property, and is preferably a coating film. Further, the barrier coat layer is preferably a cured film of a hydrolysis product of a metal alkoxide and a water-soluble polymer. The barrier coat layer can be formed by, for example, the following gas barrier coating film. The coating film is a coating film that maintains gas barrier properties in a high temperature and high humidity environment, and the general formula R ¹ _n M (OR ² ) _m (however, in the formula, R ¹ and R ² have 1 to 8 carbon atoms. Represents an organic group of, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M). It contains one or more kinds of metal alkoxides and a water-soluble polymer, and further comprises a gas barrier composition formed by polycondensation by a solgel method in the presence of a solgel method catalyst, an acid, water, and an organic solvent. It is a coating film. The composition is coated on the thin-film film on the thin-film film to provide a coating film, and heat-dried at 20 ° C. to 200 ° C. and at a temperature equal to or lower than the melting point of the thin-film film for 10 seconds to 10 minutes. Can be formed.

Further, the gas barrier composition is coated on a vapor-deposited film on the base film, and two or more coating films are laminated, at a temperature of 20 ° C. to 200 ° C. and at a temperature equal to or lower than the melting point of the base film. It may be heat-dried for 10 seconds to 10 minutes to form a composite polymer layer in which two or more layers of a gas barrier coating film are layered.

For the metal alkoxide, silicon, zirconium, titanium, aluminum, and the like can be exemplified as the metal atom represented by M in the ^{general formula R 1} _n M (OR ² ) _m. In the present invention, two or more kinds of the above alkoxides may be used in combination. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness and heat resistance of the obtained gas barrier laminated film can be improved, and deterioration of the retort resistance of the film during stretching can be avoided. Further, when alkoxysilane and titanium alkoxide are mixed and used, the thermal conductivity of the obtained gas barrier coating film is lowered, and the heat resistance is remarkably improved.

As the water-soluble polymer used in the present invention, a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be used alone. Can be used in combination with coalescence. In the present invention, by using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, physical properties such as gas barrier property, water resistance, weather resistance, and the like can be remarkably improved.

As the polyvinyl alcohol-based resin, generally, one obtained by saponifying polyvinyl acetate can be used. The polyvinyl alcohol-based resin may be a partially saponified polyvinyl alcohol-based resin in which several tens of percent of acetic acid groups remain, a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or a modified polyvinyl alcohol-based resin in which OH groups are modified. Well, it is not particularly limited.

As the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. For example, it includes, and is not particularly limited, from a partially saponified product in which several tens of mol% of acetic acid groups remain to a completely saponified product in which only a few mol% of acetic acid groups remain or no acetic acid groups remain. However, from the viewpoint of gas barrier property, the degree of saponification is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. The content of the repeating unit derived from ethylene in the above ethylene / vinyl alcohol copolymer (hereinafter, also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferable.

Further, in the present invention, a silane coupling material may be added to the barrier coat layer. For example, a silane coupling material having a reactive group such as an alkoxy group such as a methoxy group or an ethoxy group, an acetoxy group, an amino group or an epoxy group can be used.

The barrier coat layer can be produced by the following method. First, the above metal alkoxide, if necessary, a silane coupling agent, a water-soluble polymer, a sol-gel method catalyst, an acid, water, an organic solvent and the like are mixed to prepare a gas barrier composition (barrier coating liquid).

Next, the above gas barrier composition is applied onto the second chemical vapor deposition film. As a method of applying the gas barrier composition, for example, a roll coating such as a gravure roll coater, a spray coating, a spin coating, a dipping, a brush, a bar code, an applicator, or the like can be applied once or a plurality of times. A coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm can be formed.

Next, the base film coated with the gas barrier composition is heated at a temperature of 20 ° C. to 200 ° C. and a temperature equal to or lower than the melting point of the vapor-deposited film, preferably in the temperature range of 50 ° C. to 180 ° C. for 10 seconds to 10 minutes. dry. As a result, polycondensation is carried out and a barrier coat layer can be formed.

As described above, a barrier film having a barrier coat layer in which one or more barrier coat layers made of the gas barrier composition are formed on the second chemical vapor deposition film can be produced.

<Use>
The barrier film obtained by the method of 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 and electrical / electronic products such as solar cells and displays (display devices).

<Packaging material>
The barrier film obtained by the method of 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 after the weather resistance test, it is a pharmaceutical product that requires visibility of the contents and high water vapor barrier property. It can be particularly preferably used as a packaging material for pharmaceutical products.

<Manufacturing of barrier film>
[Example 1]
A biaxially stretched PET film (manufactured by Toray Co., Ltd .: U34) as a resin base material ^{was placed in a vacuum chamber of the parallel plate type plasma CVD apparatus (electrode area S: 0.083 m 2} ) described above and installed 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 base material. 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 HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus as a monomer gas for film formation as a raw material 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 electric power was set to 100 W and the film was formed. At this time, the plasma intensity E ₁ at the time of film formation was 0.40. The film formation time was 10 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. A first chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 30.4: 47.1: 22.6 was formed.

Subsequently, the resin base material on which the first chemical vapor deposition layer was formed was placed in the vacuum chamber of the parallel plate type plasma CVD apparatus described above 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 HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus as a monomer gas for film formation as a raw material 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. At this time, the plasma intensity E ₂ at the time of film formation was 1.48. The film formation time was 10 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. A second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 33.4: 65.7: 0.9 was formed to obtain a barrier film.

[Examples 2-27] [Comparative Examples 1-9]
A barrier film was obtained in the same manner as in Example 1 except that the film forming conditions shown in Table 2 were changed. However, when the flow rate of Ar was 3 sccm, the temperature of the bubbler was 30 ° C., and when the flow rate of Ar was 50 sccm, the temperature of the bubbler was 39 ° C.

[Example 28]
A biaxially stretched PET film (manufactured by Toyo Boseki Co., Ltd .: A4100) was passed as a resin base material through the roll-to-roll type plasma CVD apparatus (discharge part area S: 0.047 m ² ) described above, and the chamber was closed. After reducing the pressure to 01 Pa or less, He gas was used as a carrier gas, and HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus as a monomer gas for film formation as a raw material by bubbling. The flow rate of He gas was 100 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 103 sccm. Separately, 1500 sccm of oxygen gas was supplied, mixed with He gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 5 Pa, the electric power was set to 300 W and the film was formed. At this time, the plasma intensity E ₁ at the time of film formation was 0.75. The transport speed of the base material at the time of film formation was 2 m / min. After the film formation was completed, the discharge and gas supply were stopped, the pressure was reduced to 0.01 Pa or less, and then venting was performed to return to atmospheric pressure. A first chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 30.4: 54.7: 14.9 was formed.

Subsequently, the resin base material on which the first chemical vapor deposition layer is formed is passed through the roll-to-roll type plasma CVD apparatus described above, the chamber is closed, the pressure is reduced to 0.01 Pa or less, and then He gas is carried. As a gas, HMDSO was supplied into the vacuum chamber of the plasma CVD apparatus as a raw material film-forming monomer gas by bubbling. The flow rate of He gas was 100 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 103 sccm. Separately, 1500 sccm of oxygen gas was supplied, mixed with He gas and HMDSO, and then introduced into the vacuum chamber. After adjusting the displacement and adjusting the pressure in the vacuum chamber to 3.5 Pa, the electric power was set to 700 W and the film was formed. At this time, the plasma intensity E ₂ at the time of film formation was 2.51. The transport speed of the base material at the time of film formation was 1 m / min. After the film formation was completed, the discharge and gas supply were stopped, the pressure was reduced to 0.01 Pa or less, and then venting was performed to return to atmospheric pressure. A second chemical vapor deposition layer having a vapor deposition film composition ratio Si: O: C of 32.4: 60.9: 6.7 was formed.

Subsequently, a hydrolyzed solution of composition B prepared in advance was added to the prepared mixed solution of composition A according to the composition shown in Table 1 and stirred to obtain a colorless and transparent barrier coat solution.

Next, the resin base material on which the second chemical vapor deposition layer was formed was coated with the barrier coating liquid prepared above by a spin coating method. The conditions for spin coating were up 3 seconds + run1800 rpm 5 seconds + down 3 seconds. Then, it was heat-treated in an oven at 180 ° C. for 60 seconds to form a barrier coat layer having a thickness of about 400 nm to obtain a barrier film.

[Examples 29 to 30]
A barrier film was obtained in the same manner as in Example 28 except that the film forming conditions shown in Table 4 were changed.

[Comparative Examples 10 to 11]
A barrier film was obtained in the same manner as in Example 28 except that the film forming conditions shown in Table 4 were changed and the barrier coat 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 permeability)
The water vapor permeability of the barrier film is based on JIS K7129B using a water vapor permeability measuring machine (MOCON: PERMATRAN) or ISO 15106-5 using Tecnolox DELTA PARM. The measurement was performed in an environment of a temperature of 40 ° C. and a humidity of 90%. The measurement results were as shown in Tables 3 and 5 below.

(Measurement of total light transmittance)
The total light transmittance of the barrier film was measured using HAZE METER HM-150 manufactured by Murakami Color Research Institute Co., Ltd. in accordance with JIS K7361. The measurement results were as shown in Tables 3 and 5 below.

(Measurement of haze)
The haze of the barrier film was measured using HAZE METER HM-150 manufactured by Murakami Color Research Institute Co., Ltd. in accordance with JIS K7136. The measurement results were as shown in Tables 3 and 5 below.

(Measurement of film thickness)
The film thickness was confirmed by measuring the step difference between the portion where the chemical vapor deposition layer formed on the silicon wafer was present and the portion where the chemical vapor deposition layer was not present with a surf coder ET4000L manufactured by Kosaka Research Institute. The chemical vapor deposition layer formed by the roll-to-roll plasma CVD apparatus was embedded in a resin, and an ultrathin section was prepared from the cross section and observed with a transmission electron microscope (TEM). As an electron microscope, H-7650 manufactured by Hitachi High-Technologies Corporation was used. The measurement results were as shown in Tables 3 and 5 below.

(Composition analysis)
The element 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. Ion sputtering conditions for confirming the composition in the depth direction is set to 2.0 × ¹⁰ -2 Pa by adjusting the Ar gas amount to be introduced, and the acceleration voltage of the ion gun 0.3 kV, the emission current and 30mA .. The elemental composition at each depth was analyzed by controlling the sputtering time.

(Weather resistance test)
Using ATLAS Xenon Weather-Ometer Ci5000, according to ISO 4892-2, test cycle 120 minutes (light irradiation 102 minutes, light irradiation + water spray 18 minutes), xenon lamp illuminance 60 W / m2 (300-) The irradiation test was carried out for 120 hours under the conditions of (400 nm), a panel test temperature of 65 ° C., and a test tank temperature of 38 ° C. Irradiation was performed from the surface side of the vapor-deposited film. The measurement results were as shown in Tables 3 and 5 below.

10 Barrier film 11 Resin base material 12 First chemical vapor deposition layer 13 Second chemical vapor deposition layer

Claims (7)

A method for producing a barrier film, which comprises 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 is expressed by the following formula:
E ₁ = W ÷ (S × P × F)
0.05 ≤ E ₁ ≤ 1.20
20 ≦ W ≦ 100
(In the formula, E ₁ is the plasma intensity, W is the electric power (W) at the time of film formation, S is the electrode area (m ² ) of the film forming apparatus or the area of the discharge part (m ² ), and P. Is the pressure (Pa) at the time of film formation, and F is the total flow rate (sccm) of the gas used at the time of film formation.)
A method characterized by forming a film under conditions that satisfy the conditions. The second chemical vapor deposition layer is expressed by the following formula:
E ₂ = W ÷ (S × P × F)
E ₁ <E ₂
1.00 ≤ E ₂ ≤ 3.00
(In the formula, E ₂ is the plasma intensity, W is the electric power (W) at the time of film formation, S is the electrode area (m ² ) of the film forming apparatus or the area of the discharge part (m ² ), and P. Is the pressure (Pa) at the time of film formation, and F is the total flow rate (sccm) of the gas used at the time of film formation.)
The method according to claim 1, wherein the film is formed under the film forming conditions satisfying the above conditions. _{The method according to claim 1 or 2, wherein the thickness T 1 of} the first chemical vapor deposition layer is 10 nm or more and 1000 nm or less. The method according to any one of claims 1 to 3, _{wherein the thickness T 2 of} the second chemical vapor deposition layer is 50 nm or more and 1000 nm or less. Claim 1 is provided on the second chemical vapor deposition layer with a barrier coat layer obtained by hydrolyzing and polycondensing a barrier coat solution containing at least one alkoxide and one water-soluble polymer. The method according to any one of ~ 4. The method according to any one of claims 1 to 5, wherein the total light transmittance of the barrier film is 80% or more. The method according to any one of claims 1 to 6, wherein the haze of the barrier film is 10% or less.

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