JP2019202451A - Barrier film - Google Patents

Abstract

To provide a barrier film that has excellent gas barrier properties even after storage under a high-temperature and high-humidity environment, and suppresses deterioration in the gas barrier properties even after a Gelbo-flex test.MEANS: A barrier film according to the invention has a resin base material, a flattening layer, a chemical gas phase vapor deposition layer, and a barrier coat layer in the stated order. The flattening layer has a thickness of 0.3 μm or more and 2.5 μm or less. The flattening layer contacts the chemical gas phase vapor deposition layer on one side, which has a surface roughness Ra of 2.0 nm or less.SELECTED DRAWING: Figure 1

Description

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

  In recent years, as a barrier material against oxygen or water vapor, etc., an inorganic oxide such as silicon oxide or aluminum oxide is formed on a film substrate by vacuum deposition, sputtering, ion plating, chemical vapor deposition, or the like. The transparent gas barrier film is attracting attention. In particular, depending on the application of the barrier film, it was necessary to maintain gas barrier properties even after storage in a high temperature and high humidity environment.

  In order to maintain the high gas barrier property even after being subjected to the boil treatment and retort treatment particularly under high humidity, the specific skeletal structure and the compound in order to obtain the adhesion to the base film. A gas barrier film using a polyurethane resin containing benzene has been proposed (see Patent Document 1).

JP 2004-10656 A

  In the case of a container using a barrier film, the present inventors need to suppress deterioration of the gas barrier property even after the gelboflex test in addition to maintaining the gas barrier property after storage in a conventional high temperature and high humidity environment. I found out that there is.

  Accordingly, an object of the present invention is to provide a barrier film that has excellent gas barrier properties even after storage in a high-temperature and high-humidity environment, and that suppresses deterioration of the gas barrier properties even after a gelbo flex test.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have provided a planarizing layer having a specific thickness and a specific surface roughness Ra on a resin substrate, By laminating a phase-deposited layer and a barrier coat layer in this order, the barrier film has excellent gas barrier properties even after storage in a high-temperature and high-humidity environment, and suppresses deterioration of the gas barrier properties even after the gelbo flex test. It was found that can be provided. 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 substrate, a planarization layer, a chemical vapor deposition layer, and a barrier coat layer in this order,
The planarization layer has a thickness of 0.3 μm or more and 2.5 μm or less;
A barrier film is provided in which the surface roughness Ra on the side of the planarizing layer in contact with the chemical vapor deposition layer is 2.0 nm or less.

  In the aspect of the present invention, the chemical vapor deposition layer is preferably an inorganic oxide vapor deposition film.

  In an aspect of the present invention, the inorganic oxide vapor deposition film preferably contains silicon, oxygen, and carbon.

  In the aspect of the present invention, the chemical vapor deposition layer preferably has a thickness of 50 nm to 200 nm.

  In the aspect of the present invention, the barrier coat layer is preferably a cured film of a hydrolysis product of a metal alkoxide and a water-soluble polymer.

  In the embodiment of the present invention, the barrier coat layer preferably has a thickness of 150 nm or more and 300 nm or less.

  In the aspect of the present invention, the planarizing layer preferably contains an acrylic resin.

  In the embodiment of the present invention, it is preferably used as a packaging material for medical products / pharmaceuticals.

  ADVANTAGE OF THE INVENTION According to this invention, the barrier film which was excellent in gas barrier property even after the preservation | save in a high-temperature, high-humidity environment, and suppressed deterioration of gas barrier property after a gelbo flex test can be provided. Such a barrier film can be suitably used for applications requiring high gas barrier properties, pinhole / crack resistance, and the like, for example, medical products and pharmaceutical packaging materials.

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 includes a resin base material, a planarization layer, a chemical vapor deposition layer, and a barrier coat layer in this order.

The barrier film has excellent water vapor barrier properties, and water vapor permeability is preferably 5.0 × 10 ⁻² g / m ² / day or less, preferably 2.0 × 10 ⁻² g / m ² / day or less. Preferably, it is 1.0 × 10 ⁻² g / m ² / day or less, more preferably 8.0 × 10 ⁻³ g / m ² / day or less, and even more preferably 5.0 × 10. ⁻³ g / m ² / day or less, even more preferably 3.0 × 10 ⁻³ g / m ² / day or less, and most preferably 2.0 × 10 ⁻³ g / m ² / day or less. . If the water vapor permeability satisfies the above numerical range, it can be used as a packaging material even for applications requiring high water vapor barrier properties. The water vapor transmission rate is determined according to JIS K7129B using a water vapor transmission meter (manufactured by MOCON: PERMATRAN) or according to ISO 15106-5 using TECHNOLOX DELTA PARM. It can be measured in an environment of 40 ° C. and a humidity of 90%.

The barrier film has a water vapor permeability after storage for 120 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, preferably 5.0 × 10 ⁻² g / m ² / day or less, preferably 2.0 ×. 10 ⁻² g / m ² / day or less, preferably 1.0 × 10 ⁻² g / m ² / day or less, more preferably 8.0 × 10 ⁻³ g / m ² / day or less. More preferably 5.0 × 10 ⁻³ g / m ² / day or less, even more preferably 3.0 × 10 ⁻³ g / m ² / day or less, and most preferably 2.0 × 10 ^{−. 3} g / m ² / day or less. If the water vapor permeability after storage under the above conditions satisfies the above numerical range, it can be used as a packaging material even for applications exposed to high temperature and high humidity environments.

The barrier film preferably has a water vapor permeability after a gelboflex test in accordance with MIL B 131 (ASTM F 392) of 1.0 g / m ² / day or less, preferably 8.0 × 10 ⁻¹ g. / M ² / day or less, more preferably 5.0 × 10 ⁻¹ g / m ² / day or less, even more preferably 3.0 × 10 ⁻¹ g / m ² / day or less, and even more preferably. Is 2.0 × 10 ⁻¹ g / m ² / day or less. If the water vapor permeability after the gelboflex test satisfies the above numerical range, it is excellent in pinhole resistance and can be suitably used as a packaging material.

The barrier film has an oxygen permeability after a gelboflex test according to MIL B 131 (ASTM F 392), preferably 5.0 cc / m ² / day or less, more preferably 3.0 cc / m ² / day or less, more preferably 2.0 cc / m ² / day or less. If the oxygen permeability after the gelboflex test satisfies the above numerical range, it has excellent pinhole resistance and can be suitably used as a packaging material. The oxygen permeability can be measured in an environment having a temperature of 23 ° C. and a humidity of 85% in accordance with JIS K 7126 using an oxygen permeability measuring device (manufactured by MOCON: OX-TRAN).

  The barrier film is excellent in transparency and has a total light transmittance of preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. When the total light transmittance satisfies the above numerical range, the contents are highly visible 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 Lighting Research Co., Ltd.

  The barrier film is excellent in permeability and has a haze of preferably 10% or less, more preferably 5% or less, and further preferably 3% or less. When the haze satisfies the above numerical range, the contents are excellent in visibility when used as a packaging material. In addition, haze can be measured based on JISK7136 using HAZE METER HM-150 made from Murakami lighting laboratory.

  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 planarization layer 12, a chemical vapor deposition layer 13, and a barrier coat layer 14 in this order. Hereinafter, each layer which comprises the barrier film of this invention is demonstrated.

(Resin base material)
The resin substrate constituting the barrier film according to the present invention is not particularly limited as long as it can carry the following planarization layer and chemical vapor deposition layer, and various known resin substrates can be used.

  Examples of the resin base material include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyolefin resins such as polyethylene, polypropylene, poly-4-methyl / 1-pentene, and polybutene, and (meth) acrylic resins. , Polycarbonate resins, fluororesins, polyvinyl chloride resins, nylon resins such as nylon-6, nylon-66, and polymetaxylene adipamide, ethylene / vinyl acetate copolymers or saponified products thereof, polyvinyl alcohol, polyacrylonitrile, Examples thereof include resin films such as polystyrene, ionomer, and mixtures thereof. The resin substrate may be a single layer resin film or a laminate composed of two or more types of resin films.

  In addition, these resin films have a surface, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat, in order to improve adhesion with the following planarization layer and chemical vapor deposition layer. Surface activation treatment such as treatment or frame treatment may be performed.

  The thickness of the resin base material is not particularly limited, but is preferably 10 μm or more and 300 μm, more preferably 20 μm or more and 200 μm or less, and further preferably 50 μm or more and 200 μm or less. If the film thickness of the resin substrate is within the above range, the strength as a barrier film can be maintained.

(Flattening layer)
The planarization layer which comprises the barrier film by this invention is a layer for improving the smoothness of the resin base-material surface. The planarization layer has a surface roughness Ra (arithmetic average roughness) on the side in contact with the chemical vapor deposition layer of 2.0 nm or less, more preferably 1.5 nm or less, and further preferably 1.0 nm or less. It is. Further, the planarization layer has a surface roughness Pv (maximum valley depth) on the side in contact with the chemical vapor deposition layer, preferably 30 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less. . If the surface roughness Ra and Pv of the planarizing layer on the side in contact with the chemical vapor deposition layer satisfy the above numerical values, the adhesion with the chemical vapor deposition layer is further improved, and after storage in a high temperature and high humidity environment The gas barrier property is excellent, and deterioration of the gas barrier property can be suppressed even after the gelbo flex test. In addition, surface roughness Ra (arithmetic mean roughness) and Pv (maximum valley depth) are measured using a scanning probe microscope (manufactured by SII Nanotechnology, Nanocute SPI3800N) in accordance with JIS B 0601. Can be measured.

  The thickness of the planarization layer is 0.3 μm or more and 2.5 μm or less, preferably 0.4 μm or more and 2.0 μm or less, more preferably 0.5 μm or more and 1.5 μm or less. If the thickness of the flattening layer is within the above range, the adhesion with the chemical vapor deposition layer is further improved, the gas barrier property after storage in a high-temperature and high-humidity environment is excellent, and after the gelbo flex test In this case, deterioration of gas barrier properties can be suppressed. In addition, the thickness of the chemical vapor deposition layer can be measured using a fluorescent X-ray analyzer (manufactured by Rigaku, RIX).

  The composition of the planarizing layer is not particularly limited as long as the surface roughness Ra and Pv satisfy the above numerical values. In order to improve the visibility when used as a packaging material, it is preferable to use a highly transparent material. As the material for the planarization layer, a resin material such as the above-described thermosetting resin or thermoplastic resin used as a material for the resin base material can be used. For example, since it is easy to improve smoothness, it is preferable to use (acrylic resin, for example, acrylic acid ester, methacrylic acid ester polymethyl acrylate, polymethyl methacrylate.

  The method for forming the flattening layer is not particularly limited. For example, after applying a flattening layer forming coating solution containing at least the above resin material on the resin base material, the flattening layer is cured. Can be formed. The application of the coating liquid for forming the flattening layer is not particularly limited as long as it can be applied on the resin substrate. For example, spin coating, roll coating, spray coating, etc. It is possible to use a known coating method such as a method, a dip coating method, or a bead coating method. As for the curing method, if it is possible to cure the flattening layer forming coating liquid applied by the above method, it is appropriately selected by the above flattening layer forming coating liquid, A known curing method can be used.

  Subsequently, by pressing the formed planarization layer at a temperature equal to or higher than the glass transition temperature of the resin material, the planarization layer surface can be planarized and the surface roughness Ra and Pv can be adjusted. . The method is not particularly limited as long as the surface of the flattening layer can be flattened by pressurization. For example, the surface can be pressed by a mirror roll, a hard metal steel plate, a hard metal sphere, or the like. it can.

(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 easier to form a thick vapor deposition layer than the vapor deposition film obtained by the physical vapor deposition method (PVD method) and is excellent in flexibility. More suitable as a layer.

  The chemical vapor deposition layer is preferably an inorganic oxide vapor deposition film, and the inorganic oxide vapor deposition film preferably contains silicon, oxygen, and carbon. In the inorganic oxide vapor-deposited film, the ratio of silicon is preferably 25% or more and 40% or less, more preferably 28% or more and 37% or less, with respect to 100% of the total of three elements of silicon, oxygen, and carbon. More preferably, it is 30% or more and 35% or less. The proportion of oxygen is preferably 50% to 70%, more preferably 55% to 65%, and still more preferably 57% to 60%. The proportion of carbon is preferably 5% or more and 20% or less, more preferably 7% or more and 17% or less, and further preferably 10% or more and 15% or less. The ratio of silicon, oxygen, and carbon in the deposited film satisfies the above conditions, so it has excellent gas barrier properties even after storage in a high-temperature and high-humidity environment, and the gas barrier properties deteriorate even after the gelbo flex test. Can be suppressed.

  The thickness of the chemical vapor deposition layer is preferably 50 nm to 200 nm, more preferably 60 nm to 180 nm, still more preferably 70 nm to 170 nm, and still more preferably 80 nm to 150 nm. By satisfying the above conditions for the thickness of the chemical vapor deposition layer, it has excellent gas barrier properties even after storage in a high-temperature and high-humidity environment, and suppresses deterioration of the gas barrier properties even after the gelboflex test. Can do. In addition, the thickness of a chemical vapor deposition layer can be adjusted to a desired range by adjusting the film conveyance speed in the case of vapor deposition.

  The method for forming the chemical vapor deposition layer is not particularly limited, and examples thereof include the following methods. For example, on a resin base material, a monomer gas for film formation containing one or more organic silicon compounds is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and further, as an oxygen supply gas Further, a chemical vapor deposition layer containing silicon oxide can be formed using a plasma chemical vapor deposition method using oxygen gas or the like and using a plasma generator or the like.

  In the above, as the plasma generating apparatus, an apparatus capable of performing low-pressure plasma processing is preferable because of easy control of the plasma atmosphere and freedom of usable gas. As the low-pressure plasma processing apparatus, an ICP type plasma processing apparatus, a parallel plate type plasma processing apparatus, a roll-to-roll type plasma processing apparatus, or the like can be used. From the viewpoint of productivity, a roll-to-roll type plasma processing apparatus is preferable. As a power source used for plasma generation, a conventionally known power source such as a high frequency power source or a pulse wave power source can be used. If the frequency of the power source is in the range of 100 kHz or less, the degree of freedom of gas is high, which is preferable.

  As a mixing ratio of each gas component of the mixed gas composition for film formation, for example, monomer gas for film formation: oxygen gas: inert gas = 1: 0 to 20: 0-5 (unit: slm, standard liter minute) A mixed gas composition for film formation having a gas composition ratio of (substantially) 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 thereto. It is possible to form a vapor deposition film containing them. By adjusting the mixing ratio of each gas component of the mixed gas composition for film formation, the ratio of silicon, oxygen, and carbon contained in the chemical vapor deposition layer can be appropriately adjusted.

  Examples of the organosilicon compound constituting the monomer gas for film formation include 1.1.3.3-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 organosilicon compounds, it is particularly preferable to use 1.1.3-3 tetramethyldisiloxane or hexamethyldisiloxane as a raw material from the viewpoints of handleability, characteristics of the formed continuous film, and the like. Moreover, as an inert gas, argon gas, helium gas, etc. can be used, for example.

(Barrier coat layer)
The barrier coat layer constituting the barrier film according to the present invention is a layer having gas barrier properties, and is preferably a coating film. Furthermore, 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 gas barrier coating film is a coating film that maintains gas barrier properties in a high-temperature and high-humidity environment, and has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² have 1 to 8 represents an organic group, 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 an atomic valence of M). A gas barrier composition comprising at least one metal alkoxide and a water-soluble polymer, and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent. This is a coating film.

In the general formula R ¹ _n M (OR ² ) _m , R ¹ is an alkyl group having 1 to 8, preferably 1 to 5, more preferably 1 to 4 carbon atoms which may have a branch. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group, etc. Can be mentioned.

In the general formula R ¹ _n M (OR ² ) _m , R ² is an alkyl group having 1 to 8, more preferably 1 to 5, and particularly preferably 1 to 4 carbon atoms which may have a branch. Yes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and the like can be mentioned. When a plurality of (OR ² ) are present in the same molecule, (OR ² ) may be the same or different.

Examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, and aluminum.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one of alkoxide partial hydrolyzate and alkoxide hydrolysis condensate can be used. The partial hydrolyzate is not limited to the one in which all of the alkoxy groups are hydrolyzed, and may be one in which one or more are hydrolyzed, or a mixture thereof, and further a hydrolysis condensate. As a dimer or more of a partially hydrolyzed alkoxide, specifically, a dimer or hexamer may be used.

In this invention, the alkoxysilane whose M is Si can be used suitably as an alkoxide represented by the said general formula R _< ¹ _> nM (OR _< ² _> ) _m . Suitable alkoxysilanes include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC _4). H _{9) 4,} methyltrimethoxysilane _{CH 3 Si (OCH 3) 3} , methyltriethoxysilane _{CH 3 Si (OC 2 H 5} ) 3, dimethyldimethoxysilane _{(CH 3) 2 Si (OCH} 3) 2, dimethyldi And ethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ . In the present invention, a polycondensation product of these alkoxysilanes can also be used. Specifically, for example, polytetramethoxysilane, polytetraemethoxysilane and the like can be used.

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

  As the polyvinyl alcohol resin, those obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetic acid groups remain, completely saponified polyvinyl alcohols in which no acetic acid groups remain, or modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited.

  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.

  Furthermore, as an organic solvent used in said gas-barrier composition, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol etc. can be used, for example. The polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is preferably handled in a state of being dissolved in a coating solution containing the alkoxide, silane coupling agent, or the like. It can be selected appropriately. For example, when a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in combination, n-butanol is preferably used.

  The barrier coat layer can be produced by the following method. First, the above-described 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 solution).

  Next, the gas barrier composition is applied on the chemical vapor deposition layer. Examples of the method for applying the gas barrier composition include application means such as a roll coat such as a gravure roll coater, spray coat, spin coat, dipping, brush, bar code, applicator and the like.

  Next, the film coated with the gas barrier composition is heated and dried for 10 seconds to 10 minutes at a temperature of 20 ° C. to 200 ° C. and a temperature not higher than the melting point of the deposited film, preferably 50 ° C. to 180 ° C. . Thereby, polycondensation is performed and a barrier coat layer can be formed. In addition, the gas barrier composition is applied on the chemical vapor deposition layer so as to overlap two or more coating films, and at a temperature of 20 ° C. to 200 ° C. and below the melting point of the resin substrate. You may heat-dry for 10 second-10 minutes, and you may form the composite polymer layer which laminated | stacked two or more gas barrier coating films. As described above, one to two or more barrier coat layers made of the gas barrier composition can be formed.

  The thickness of the barrier coat layer is preferably 150 nm or more and 300 nm or less, and more preferably 180 nm or more and 250 nm or less. When the thickness of the barrier coat layer is within the above range, the gas barrier property after storage in a high temperature and high humidity environment is excellent, and deterioration of the gas barrier property can be suppressed even after the gelbo flex test.

<Application>
The barrier film according to the present invention can be applied to products in various fields that require high gas barrier properties. For example, it can be used for packaging materials, electrical / electronic products such as solar cells, organic light emitting diodes, and display devices. In particular, the barrier film according to the present invention can be used as a packaging material for medical products, pharmaceuticals, cosmetics, chemicals, foods and drinks, and the like. The barrier film has excellent gas barrier properties even after storage in a high-temperature and high-humidity environment, and suppresses deterioration of the gas barrier properties even after the gelboflex test, so that a high gas barrier property is required. It can be particularly preferably used as a packaging material for medical products and pharmaceuticals.

<Manufacture of barrier film>
[Example 1]
A biaxially stretched PET film (manufactured by Mitsubishi Chemical Corporation, trade name: T600W, thickness 23 μm) was prepared as a resin base material. Next, a planarizing layer (main component: acrylic resin, thickness 0.5 μm, surface roughness Ra 0.7 nm, Pv 8.0 nm) was provided on one surface of the PET film. In addition, Ra (arithmetic mean roughness) and Pv (maximum valley depth) of the surface roughness of the planarizing layer are in accordance with MIL B 131 (ASTM F 392), a scanning probe microscope (SII Nanotechnology). Measurement was performed in a scanning area of 5 μm using Nanocute SPI3800N).

Subsequently, on the planarized layer of the PET film, using a roll-to-roll type plasma CVD processing apparatus, a vapor deposition film composition ratio Si: O: C is 31:59:10 under the following conditions. A layer (thickness 160 nm) was formed. In addition, the thickness of the chemical vapor deposition layer was measured using a fluorescent X-ray analyzer (manufactured by Rigaku, RIX).
(Chemical vapor deposition layer deposition conditions 1)
・ Power input 0.7kW
・ Raw gas composition HMDSO
・ He / Mn / O ₂ 100/100/1500 sccm
・ Ar for electrode 100 sccm
・ Film pressure 3.5Pa
・ Film thickness 160nm
・ Film transport speed 0.5m / min

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

  Next, the gas barrier composition prepared above was coated on the chemical vapor deposition layer of the PET film by a direct gravure method. Then, it heat-processed at 140 degreeC for 60 second, and formed the gas barrier coating film of thickness 200nm (dry operation state), and obtained the barrier film.

[Example 2] to [Example 6], [Comparative Example 1]
A barrier film was produced in the same manner as in Example 1 except that the thickness and surface roughness of the planarization layer and the thickness of the chemical vapor deposition layer were as shown in Table 2 below.

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

(Measurement of water vapor permeability 1)
The water vapor permeability of the barrier film is measured according to JIS K7129B using a water vapor permeability measuring device (manufactured by MOCON: PERMATRAN) or according to ISO 15106-5 using Tektronox DELTA PARM. Measurement was performed in an environment of a temperature of 40 ° C. and a humidity of 90%. The measurement results were as shown in Table 2 below.

(Measurement of water vapor permeability 2)
The barrier film was stored for 120 hours in an environment at a temperature of 85 ° C. and a humidity of 85%. Subsequently, the water vapor permeability of the barrier film after storage was measured in the same manner as in the above measurement 1 of water vapor permeability. The measurement results were as shown in Table 2 below.

(Measurement of water vapor permeability 3)
The gel film was subjected to a gelbo flex test with a number of flexing times of 50 in accordance with MIL B 131 (ASTM F 392) using a gelbo flex tester manufactured by Tester Sangyo in consideration of actual use conditions. Subsequently, the water vapor transmission rate of the barrier film after the gelboflex test was measured in the same manner as in the measurement 1 of the water vapor transmission rate. The measurement results were as shown in Table 2 below.

(Measurement of oxygen permeability)
The gel film was subjected to a gelbo flex test with a number of flexing times of 50 in accordance with MIL B 131 (ASTM F 392) using a gelbo flex tester manufactured by Tester Sangyo in consideration of actual use conditions. Subsequently, the oxygen permeability of the barrier film after the gelboflex test was measured at a temperature of 23 ° C. and a humidity of 85% in accordance with JIS K 7126 using an oxygen permeability measuring device (manufactured by MOCON: OX-TRAN). Measured in the environment. The measurement results were as shown in Table 2 below.

Explanation of sign

DESCRIPTION OF SYMBOLS 10 Barrier film 11 Resin base material 12 Planarization layer 13 Chemical vapor deposition layer 14 Barrier coat layer

Claims (8)

A barrier film comprising a resin substrate, a planarization layer, a chemical vapor deposition layer, and a barrier coat layer in this order,
The planarization layer has a thickness of 0.3 μm or more and 2.5 μm or less;
The barrier film whose surface roughness Ra of the side which contacts the chemical vapor deposition layer of the said planarization layer is 2.0 nm or less.   The barrier film according to claim 1, wherein the chemical vapor deposition layer is an inorganic oxide vapor deposition film.   The barrier film according to claim 2, wherein the inorganic oxide vapor deposition film contains silicon, oxygen, and carbon.   The barrier film as described in any one of Claims 1-3 whose thickness of the said chemical vapor deposition layer is 50 nm or more and 200 nm or less.   The barrier film according to any one of claims 1 to 4, wherein the barrier coat layer is a cured film of a hydrolysis product of a metal alkoxide and a water-soluble polymer.   The barrier film as described in any one of Claims 1-5 whose thickness of the said barrier-coat layer is 150 nm or more and 300 nm or less.   The barrier film as described in any one of Claims 1-6 in which the said planarization layer contains acrylic resin.   The barrier film as described in any one of Claims 1-7 used for the packaging material for medical supplies and pharmaceuticals.

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