JP6930109B2 - 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, an intermediate layer, and a barrier 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 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.

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 plastics 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. It is also desired to use a barrier film in applications that require moisture and heat resistance.

Japanese Unexamined Patent Publication No. 5-345383

The present invention has been made in view of the above background technology, and an object of the present invention is to provide a barrier film having excellent water adhesion resistance and excellent water vapor barrier property even after storage in a high temperature and high humidity environment. To provide.

As a result of diligent studies to solve the above problems, the present inventors have formed an intermediate layer composed of a vapor-deposited film having a specific composition on a resin base material, and then a reaction product of a metal oxide and a phosphorus compound. It has been found that by further forming a barrier layer containing the above, it is possible to provide a barrier film having excellent water adhesion resistance 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 having a resin base material, an intermediate layer, and a barrier layer in this order.
The intermediate layer is a thin-film film containing silicon, oxygen, and carbon, and the ratio C of carbon is 5% or more and 30% with respect to a total of 100% of the three elements of silicon, oxygen, and carbon in the thin-film film. Is below
A barrier film is provided in which the barrier layer contains a reaction product of a metal oxide and a phosphorus compound.

In the aspect of the present invention, it is preferable that the resin base material is a polyolefin resin base material or a polyester resin base material.

In the aspect of the present invention, it is preferable that the metal oxide is an aluminum oxide.

In the aspect of the present invention, it is preferable that the phosphorus compound is at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphoric acid and derivatives thereof.

In the aspect of the present invention, the barrier layer is selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, salt of polyacrylic acid, polymethacrylic acid and salt of polymethacrylic acid. It is preferable to further contain at least one polymer to be used.

In the aspect of the present invention, it is preferable that the vapor deposition film is a chemical vapor deposition film.

In the aspect of the present invention, the barrier film preferably has a water vapor transmission rate of 9.0 × ^10-2 g / m ² / day or less.

^{In the embodiment of the present invention, the barrier film has a water vapor transmission rate of 9.0 × 10-2} g / m ² / day or less after being stored for 500 hours in an environment of a temperature of 60 ° C. and a humidity of 90%. Is preferable.

In the aspect of the present invention, it is preferable that the barrier film is for a packaging material.

According to the present invention, it is possible to provide a barrier film having excellent water adhesion resistance 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 as a packaging material or the like.

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, an intermediate layer, and a barrier layer in this order.

The barrier film has excellent steam barrier properties and has a steam permeability of preferably 9.0 × 10 ^-2 g / m ² / day or less, more preferably 8.0 × 10 ^-2 g / m ² / day. It is less than or equal to day, more preferably 7.0 × 10 ^-2 g / m ² / day or less, and even more preferably 6.0 × 10 ^-2 g / m ² / day or less. If the water vapor transmission rate satisfies the above numerical range, it can be used as a packaging material even in applications requiring a high degree of water vapor barrier property. The water vapor transmission rate is measured using a water vapor transmission rate measuring machine (MOCON: PERMATRAN) in accordance with JIS K7129B or in Teknolex's DELTA PARM in accordance with ISO 15106-5. be able to.

^{The barrier film has a water vapor transmission rate of preferably 9.0 × 10 -2} g / m ² / day or less after storage for 500 hours in an environment of a temperature of 60 ° C. and a humidity of 90%, and more preferably 8. It is 0 × 10 ^-2 g / m ² / day or less, more preferably 7.0 × 10 ^-2 g / m ² / day or less, and even more preferably 6.0 × 10 ^-2 g / m ² / day or less. It is as follows. If the water vapor transmission rate after storage under the above conditions satisfies the above numerical range, it can be suitably used as a packaging material even in applications exposed to a high temperature and high humidity environment.

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, an intermediate layer 12, and a barrier 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 intermediate layer (deposited film), 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, and polyimide. 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 polyamides such as polymethoxylen adipamide, polyvinyl chloride, ethylene / vinyl acetate copolymers or saponates thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonates, polystyrenes, ionomers, fluororesins, or mixtures thereof. In particular, thermoplastic resins having good stretchability and transparency, such as polyolefin resins and polyester resins, are preferable. The resin base material made of these thermoplastic resins may be a single layer or a laminate made of two or more kinds of thermoplastic resins, depending on the use of the barrier film. Further, in order to improve the adhesiveness of these resin substrates with the following vapor-film deposition film, the surface thereof is subjected to, for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coating treatment, frame treatment and the like. The surface activation treatment may be performed.

<Middle class>
The intermediate layer constituting the barrier film according to the present invention is a vapor-deposited film having the following composition. The vapor-deposited film may be a single layer or a multi-layer. In the present invention, the vapor deposition film is preferably a chemical vapor deposition film formed by a chemical vapor deposition method (CVD method). Compared with the vapor deposition film obtained by the physical vapor deposition method (PVD method), the chemical vapor deposition film is easier to form a thick film vapor deposition layer and has excellent flexibility. Adhesion can be improved.

The vapor-deposited film contains silicon, oxygen, and carbon. The vapor-deposited film has a carbon ratio C of 5% or more and 30% or less, preferably 7% or more and 28% or less, more preferably, with respect to a total of 100% of the three elements of silicon, oxygen, and carbon. It is 10% or more and 25% or less, and more preferably 13% or more and 23% or less. The ratio Si of silicon is preferably 10% or more and 35% or less, more preferably 15% or more and 34% or less, further preferably 20% or more and 33% or less, and further preferably 22% or more and 32% or less. Is. The ratio O of oxygen is preferably 35% or more and 60% or less, more preferably 40% or more and 57% or less, and further preferably 45% or more and 55% or less. When the ratio C of carbon in the vapor-deposited film satisfies the above condition, the followability to the heat elongation of the resin base material during the heat treatment is improved, and the water vapor barrier property is improved even after storage in a high temperature and high humidity environment. Excellent for. Further, when the ratio Si of silicon and the ratio O of oxygen satisfy the above conditions, the water vapor barrier property is further excellent.

The thickness T of the thin-film deposition film is preferably 5 nm or more and 100 nm or less, and more preferably 10 nm or more and 50 nm or less. When the thickness of the vapor-deposited film satisfies the above conditions, the barrier film has excellent water vapor barrier property even after storage in a high-temperature and high-humidity environment. The thickness of the thin-film deposition film can be adjusted to a desired range by adjusting the film transport speed during vapor deposition.

The chemical vapor deposition vapor deposition film can be formed as an example as follows. Specifically, a film-forming monomer gas containing at least one organic silicon compound is used as a raw material on a resin base material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is further used. A chemical vapor deposition film containing silicon oxide can be formed by using an oxygen gas or the like as a supply gas and using a plasma chemical vapor deposition method using a plasma generator or the like.

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

The mixing ratio of each gas component of the mixed gas composition for film formation is, for example, monomer gas for film formation: oxygen gas: inert gas = 1: 0 to 20:00 to 5 (unit: slm, standard liter minute). A mixed gas composition for film formation or the like having a gas composition ratio of (omitted) 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 such as carbon, hydrogen, silicon or oxygen is chemically bonded to the silicon oxide. The vapor-deposited film contained therein can be formed by the above. By adjusting the mixing ratio of each gas component of the mixed gas composition for film formation, the ratio of silicon, oxygen, and carbon contained in the chemical vapor deposition film can be appropriately adjusted.

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

In order to further improve the adhesion between the resin base material and the barrier layer below, the surface of the intermediate layer is subjected to surface activity such as corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coating treatment, frame treatment and the like. The conversion process may be performed.

<Barrier layer>
The barrier layer constituting the barrier film according to the present invention contains a reaction product (R) of a metal oxide (A) and a phosphorus compound (B). The barrier layer may further contain the following polymer (C). Each component contained in these barrier layers will be described in detail below.

The metal oxide (A) may be a hydrolyzed condensate of the compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic group include X ^{1 of} the formula (I) described later.

The hydrolyzed condensate of the above compound (L) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolyzed condensate of compound (L) may be referred to as "metal oxide (A)". That is, in this specification, "metal oxide (A)" can be read as "hydrolyzed condensate of compound (L)", and "hydrolyzed condensate of compound (L)" can be read as "metal". It can be read as "oxide (A)".

The barrier layer has a structure in which particles of the metal oxide (A) are bonded to each other via a phosphorus atom derived from the phosphorus compound (B). The form bonded via a phosphorus atom includes a form bonded via an atomic group containing a phosphorus atom. The barrier layer may partially contain the metal oxide (A) and / or the phosphorus compound (B) that are not involved in the reaction.

When the metal compound reacts with the phosphorus compound, the metal atom (M) constituting the metal compound and the phosphorus atom (P) derived from the phosphorus compound are represented by MOP in which they are bonded via an oxygen atom (O). The bond that is created is generated.

In the barrier layer, the shape of each particle of the metal oxide (A) is not particularly limited, and examples thereof include spherical, flat, polyhedral, fibrous, and needle-like shapes, which are fibrous or needle-like. The shape of the above is preferable because it is more excellent in water vapor barrier property. The barrier layer may have only particles having a single shape, or may have particles having two or more different shapes. Further, the size of the particles of the metal oxide (A) is not particularly limited, and those having a nanometer size to a submicron size can be exemplified, but since they are superior in water vapor barrier property and transparency, the metal oxide (A) ( The size of the particles of A) is preferably in the range of 1 to 100 nm as an average particle size. When the barrier layer has the above-mentioned fine structure, the water vapor barrier property of the barrier film is improved.

The fine structure of the barrier layer as described above can be confirmed by observing the cross section of the barrier layer with a transmission electron microscope (TEM). The particle size of each particle of the metal oxide (A) in the barrier layer is perpendicular to the maximum length of each particle on the longest axis in the cross-sectional observation image of the barrier layer obtained by a transmission electron microscope (TEM). It can be obtained as the average value of the maximum lengths of the particles on the same axis, and the average particle size can be obtained by averaging the particle sizes of 10 particles arbitrarily selected in the cross-sectional observation image.

In the barrier layer, as the bond form between each particle of the metal oxide (A) and the phosphorus atom, for example, the metal atom (M) and the phosphorus atom (P) constituting the metal oxide (A) are oxygen atoms ( The morphology combined via O) can be mentioned. The particles of the metal oxide (A) may be bonded to each other via a phosphorus atom (P) derived from one molecule of phosphorus compound (B), but phosphorus derived from two or more molecules of phosphorus compound (B) may be bonded to each other. It may be bonded via an atom (P). As a specific bonding form between the particles of the two metal oxides (A) that are bonded, the metal atom constituting the particles of one of the bonded metal oxides (A) is represented as (Mα). When the metal atom constituting the particle of the other metal oxide (A) is represented as (Mβ), for example, the bond form of (Mα) -OPO- (Mβ); (Mα) -OP- [ _{OP] Bonding form of n-} O- (Mβ); Binding form of (Mα) -OPZ-P-O- (Mβ); (Mα) -OPZ-P- [ O-P-Z-P] Examples include the binding form of _{n-O- (Mβ).} In the above example of the bond form, n represents an integer of 1 or more, and Z represents a group of constituent atoms existing between two phosphorus atoms when the phosphorus compound (B) has two or more phosphorus atoms in the molecule. The description of other substituents bonded to the phosphorus atom is omitted. In the barrier layer, it is preferable that the particles of one metal oxide (A) are bonded to the particles of a plurality of other metal oxides (A) from the viewpoint of the water vapor barrier property of the obtained barrier film.

(Metal oxide (A))
The metal atoms constituting the metal oxide (A) (they may be collectively referred to as "metal atom (M)") have a valence of 2 or more (for example, 2 to 4 valences or 3 to 4 valences). ), Specifically, for example, a metal of Group 2 of the periodic table such as magnesium and calcium; a metal of Group 12 of the periodic table such as zinc; a metal of Group 13 of the periodic table such as aluminum. Metals; metals of Group 14 of the periodic table such as silicon; transition metals such as titanium and zirconium can be mentioned. Although silicon may be classified as a metalloid, silicon is included in the metal in the present specification. The metal atom (M) constituting the metal oxide (A) may be one kind or two or more kinds. Among these, the metal atom (M) constituting the metal oxide (A) is selected because it is easy to handle for producing the metal oxide (A) and the obtained barrier film has a more excellent water vapor barrier property. It is preferably at least one selected from the group consisting of aluminum, titanium and zirconium, and aluminum is particularly preferable.

The total ratio of aluminum, titanium and zirconium to the metal atom (M) is 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. You may. The proportion of aluminum in the metal atom (M) may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%.

As the metal oxide (A), those produced by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method can be used, and the shape and size of the obtained metal oxide (A) can be used. Considering the controllability of the metal and the production efficiency, those produced by the liquid phase synthesis method are preferable.

In the liquid phase synthesis method, a compound (L) in which a hydrolyzable characteristic group is bonded to a metal atom (M) is used as a raw material and hydrolyzed and condensed to obtain a hydrolyzed condensate of the compound (L). The metal oxide (A) can be synthesized. Further, in producing the hydrolyzed condensate of the compound (L) by the liquid phase synthesis method, in addition to the method using the compound (L) itself as a raw material, the compound (L) is partially hydrolyzed (L). Partial hydrolyzate of L), complete hydrolyzate of compound (L) obtained by completely hydrolyzing compound (L), portion of compound (L) obtained by partially hydrolyzing and condensing compound (L). Metal oxidation can also be achieved by condensing a hydrolyzed condensate, a partial condensate of a complete hydrolyzate of compound (L), or a mixture of two or more of these as a raw material and condensing or hydrolyzing this. The thing (A) can be manufactured. The metal oxide (A) thus obtained is also referred to as "a hydrolyzed condensate of the compound (L)" in the present specification. The type of the above hydrolyzable characteristic group (functional group) is not particularly limited, and examples thereof include a halogen atom (F, Cl, Br, I, etc.), an alkoxy group, an acyloxy group, a diacylmethyl group, a nitro group and the like. However, since the reaction is excellent in controllability, a halogen atom or an alkoxy group is preferable, and an alkoxy group is more preferable.

The compound (L) preferably contains ^{at least one compound (L 1} ) represented by the following formula (I) because the reaction can be easily controlled and the obtained barrier film has excellent barrier properties.
M ¹ X ¹ _m R ¹ _(nm) (I)
[In formula (I), M ¹ is a metal atom selected from the group consisting of Al, Ti and Zr. X ¹ is selected from the group consisting of F, Cl, Br, I, R ² O-, R ³ C (= O) O-, (R ⁴ C (= O)) ₂ CH- and NO _3. R ¹ , R ² , R ³ and R ⁴ are selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group, respectively. In formula (I), when a plurality of X ¹ are present, they X ¹ may be different may be identical or different. In formula (I), when a plurality of R ¹ are present, they R ¹ may be different may be identical or different. In formula (I), when a plurality of R ² are present, they R ² may be different may be identical or different. In formula (I), when a plurality of R ³ are present, they R ³ may be different may be identical or different. In formula (I), when a plurality of R ⁴ are present, they R ⁴ may be different may be identical or different. n is equal to the valence of ^{M 1.} m represents an integer of 1 to n. ]

Examples of the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, s-butyl group, t-butyl group and 2-ethylhexyl. Group etc. can be mentioned. Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a benzyl group, a phenethyl group, a trityl group and the like. Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group, a naphthyl group, a tolyl group, a xsilyl group, a mesitylene group and the like. Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ include a vinyl group, an allyl group and the like. R ¹ is preferably, for example, an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. X ¹ is preferably F, Cl, Br, I, R ² O−. In a preferred example of compound (L ^{1 ), X 1} is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O−) and m is n (M ¹ ). Atomic value). Since the ease of handling for producing the metal oxide (A) and the water vapor barrier property of the obtained barrier film are more excellent, M ¹ is preferably Al, Ti or Zr, and particularly Al. preferable. In an example of compound (L ^{1 ), X 1} is a halogen atom (F, Cl, Br, I) or an alkoxy group (R ² O−) having 1 to 4 carbon atoms, and m is an n (M ¹ atom). Equal to valence), M ¹ is Al.

Specific examples of the compound (L ¹ ) include, for example, aluminum chloride, aluminum triethoxydo, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tris-butoxide, aluminum trit-butoxide, Aluminum compounds such as aluminum triacetate, aluminum acetylacetonate, aluminum nitrate; titanium tetraisopropoxide, titanium tetranormalbutoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxyde, titanium tetraethoxydo, titanium acetylacetate. Titanium compounds such as nate; examples thereof include zirconium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide, and zirconium tetraacetylacetonate. Among these, as the compound (L ¹ ), at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable. One type of compound (L ¹ ) may be used alone, or two or more types may be used in combination.

As long as the effects of the present invention can be obtained, ^{the ratio of the compound (L 1} ) to the compound (L) is not particularly limited. The ratio of the compound other than the compound (L ¹ ) to the compound (L) is, for example, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 0 mol%. In one example, compound (L) consists ^{only of compound (L 1} ).

The compound (L ^{) other than the compound (L 1} ) is not particularly limited as long as the effects of the present invention can be obtained, but for example, the above-mentioned hydrolyzable properties of metal atoms such as magnesium, calcium, zinc and silicon can be obtained. Examples thereof include compounds to which groups are bonded. Although silicon may be classified as a metalloid, silicon is included in the metal in the present specification.

When the compound (L) is hydrolyzed, at least a part of the hydrolyzable characteristic groups of the compound (L) is replaced with a hydroxyl group. Further, the hydrolyzate is condensed to form a compound in which a metal atom (M) is bonded via an oxygen atom (O). When this condensation is repeated, a compound that can be regarded as a metal oxide is formed. A hydroxyl group is usually present on the surface of the metal oxide (A) thus formed.

In the present specification, an oxygen atom bonded only to the metal atom (M), such as the oxygen atom (O) in the structure represented by MOM, with respect to the number of moles of the metal atom (M) ( For example, the ratio of the number of moles (excluding the oxygen atom bonded to the metal atom (M) and the hydrogen atom (H) such as the oxygen atom (O) in the structure represented by MOH) ([ A compound in which the number of moles of an oxygen atom (O) bonded only to a metal atom (M)] / [number of moles of a metal atom (M)]) is 0.8 or more is included in the metal oxide (A). And. The ratio of the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, and further preferably 1.1 or more. The upper limit of the above ratio is not particularly limited, but when the valence of the metal atom (M) is n, it is usually represented by n / 2.

In order for the above hydrolysis condensation to occur, it is important that the compound (L) has a hydrolyzable characteristic group (functional group). If these groups are not bonded, the hydrolysis condensation reaction does not occur or becomes extremely slow, which makes it difficult to prepare the desired metal oxide (A).

The hydrolyzed condensate can be produced from a specific raw material, for example, by a method adopted in a known sol-gel method. The raw materials include compound (L), a partial hydrolyzate of compound (L), a complete hydrolyzate of compound (L), a partial hydrolysis condensate of compound (L), and a complete hydrolysis of compound (L). At least one selected from the group consisting of condensed parts of a substance (hereinafter, may be referred to as "compound (L) -based component") can be used. These raw materials may be produced by a known method or commercially available ones may be used. Although not particularly limited, for example, a condensate obtained by hydrolyzing and condensing about 2 to 10 compounds (L) can be used as a raw material. Specifically, for example, a product obtained by hydrolyzing and condensing aluminum triisopropoxide to form a condensate of 2 to 10 dimers can be used as a part of the raw material.

The number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions for condensing or hydrolyzing the compound (L) -based components. For example, the number of molecules to be condensed can be controlled by the amount of water, the type and concentration of the catalyst, the temperature and time at which condensation or hydrolysis condensation occurs, and the like.

As described above, the barrier layer contains the reaction product (R), and the reaction product (R) is a reaction product formed by at least the reaction of the metal oxide (A) and the phosphorus compound (B). be. Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B). The metal oxide (A) to be mixed with the phosphorus compound (B) (immediately before being mixed) may be the metal oxide (A) itself or a composition containing the metal oxide (A). It may be in the form of an object. In a preferred example, the metal oxide (A) is mixed with the phosphorus compound (B) in the form of a liquid (solution or dispersion) obtained by dissolving or dispersing the metal oxide (A) in a solvent.

Preferred methods for producing a solution or dispersion of the metal oxide (A) are described below. Here, a method of producing the dispersion liquid will be described by taking the case where the metal oxide (A) is aluminum oxide (alumina) as an example, but the same applies to the production of solutions and dispersion liquids of other metal oxides. Manufacturing method can be adopted. A preferable dispersion of alumina can be obtained by hydrolyzing and condensing aluminum alkoxide in an aqueous solution whose pH has been adjusted with an acid catalyst, if necessary, to form an alumina slurry, which is ligated in the presence of a specific amount of acid. Can be done.

The temperature of the reaction system when hydrolyzing and condensing aluminum alkoxide is not particularly limited. The temperature of the reaction system is usually in the range of 2 to 100 ° C. When water comes into contact with aluminum alkoxide, the temperature of the liquid rises, but as the hydrolysis progresses, alcohol is produced as a by-product, and when the boiling point of the alcohol is lower than that of water, the alcohol volatilizes and the temperature of the reaction system rises. It may not rise above the boiling point of alcohol. In such a case, the growth of alumina may be slowed down, so it is effective to heat to around 95 ° C. to remove the alcohol. The reaction time differs depending on the reaction conditions (presence or absence of acid catalyst, amount, type, etc.). The reaction time is generally in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably in the range of 0.1 to 6 hours. Further, the reaction can be carried out in an atmosphere of various gases such as air, carbon dioxide, nitrogen and argon.

The amount of water used in the hydrolysis condensation is preferably 1 to 200 mol times, more preferably 10 to 100 mol times with respect to the aluminum alkoxide. If the amount of water is less than 1 mol, hydrolysis does not proceed sufficiently, which is not preferable. On the other hand, if it exceeds 200 mol times, the production efficiency is lowered and the viscosity is increased, which is not preferable. When a component containing water (for example, hydrochloric acid or nitric acid) is used, it is preferable to determine the amount of water used in consideration of the amount of water introduced by the component.

As the acid catalyst used for hydrolysis condensation, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid and the like can be used. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are preferable, and nitric acid and acetic acid are more preferable. When an acid catalyst is used during hydrolysis condensation, it is preferable to use an amount suitable for the type of acid so that the pH before hydrolysis condensation is in the range of 2.0 to 4.0.

The alumina slurry obtained by hydrolysis condensation can be used as it is as an alumina dispersion, but it is transparent by heating the obtained alumina slurry in the presence of a specific amount of acid to deflocculate it. An alumina dispersion having excellent viscosity stability can be obtained.

As the acid used at the time of defibration, monovalent inorganic acids such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid and propionic acid and organic acids can be used. Among these, nitric acid, hydrochloric acid and acetic acid are preferable, and nitric acid and acetic acid are more preferable.

When nitric acid or hydrochloric acid is used as the acid at the time of defibration, the amount thereof is preferably 0.001 to 0.4 mol times and 0.005 to 0.3 mol times the aluminum atom. More preferred. If it is less than 0.001 mol times, problems such as insufficient progress of gelatinization or a very long time may occur. Further, when it exceeds 0.4 mol times, the stability of the obtained alumina dispersion with time tends to decrease.

On the other hand, when acetic acid is used as the acid at the time of defibration, the amount thereof is preferably 0.01 to 1.0 mol times and 0.05 to 0.5 mol times with respect to the aluminum atom. More preferred. If it is less than 0.01 mol times, problems such as insufficient progress of gelatinization or a very long time may occur. Further, when it exceeds 1.0 mol times, the stability of the obtained alumina dispersion with time tends to decrease.

The acid present at the time of gelatinization may be added at the time of hydrolysis condensation, but if the acid is lost when removing the alcohol by-produced by hydrolysis condensation, the amount may be in the above range. It is preferable to add it again.

By performing gluing in the range of 40 to 200 ° C., gluing is performed in a short time with an appropriate amount of acid used, and an alumina dispersion having a predetermined particle size and excellent viscosity stability is produced. be able to. If the temperature at the time of gluing is less than 40 ° C, it takes a long time to glue, and if it exceeds 200 ° C, the amount of increase in gluing speed by raising the temperature is small, while the high pressure resistant container It is not preferable because it requires such as and is economically disadvantageous.

After the gelatinization is completed, a dispersion of alumina having a predetermined concentration can be obtained by diluting with a solvent or concentrating by heating, if necessary. However, in order to suppress thickening and gelation, it is preferable to carry out heat concentration under reduced pressure at 60 ° C. or lower.

The metal oxide (A) to be mixed with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) preferably contains substantially no phosphorus atom. However, for example, due to the influence of impurities in the preparation of the metal oxide (A), it is used for mixing with the phosphorus compound (B) (when used as a composition, the composition containing the phosphorus compound (B)). A small amount of phosphorus atoms may be mixed in the metal oxide (A). Therefore, the metal oxide (A) to be mixed with the phosphorus compound (B) (composition containing the phosphorus compound (B) when used as a composition) within a range in which the effect of the present invention is not impaired. May contain a small amount of phosphorus atoms. The content of phosphorus atoms contained in the metal oxide (A) to be mixed with the phosphorus compound (B) (composition containing the phosphorus compound (B) when used as a composition) has a water vapor barrier property. Since a barrier film having excellent stability can be obtained, the number of moles of all the metal atoms (M) contained in the metal oxide (A) should be 30 mol% or less based on the number of moles (100 mol%). It is preferably 10 mol% or less, more preferably 5 mol% or less, particularly preferably 1 mol% or less, and may be 0 mol%.

The barrier layer has a specific structure in which particles of the metal oxide (A) are bonded to each other via a phosphorus atom derived from the phosphorus compound (B), and the particles of the metal oxide (A) in the barrier layer have a specific structure. The shape and size of the particles and the shape and size of the particles of the metal oxide (A) to be mixed with the phosphorus compound (B) (the composition containing the phosphorus compound (B) when used as a composition). May be the same or different. That is, the particles of the metal oxide (A) used as the raw material of the barrier layer may change in shape and size in the process of forming the barrier layer. In particular, when the barrier layer is formed using the coating liquid (U) described later, the barrier layer is formed in the coating liquid (U) or in the liquid (S) described later that can be used to form the barrier layer, or coating. The shape and size may change in each step after the liquid (U) is applied onto the base material (X).

(Phosphorus compound (B))
The phosphorus compound (B) contains a site capable of reacting with the metal oxide (A), and typically contains a plurality of such sites. In a preferred example, the phosphorus compound (B) contains 2 to 20 such sites (atomic groups or functional groups). Examples of such sites include sites capable of reacting with functional groups (eg, hydroxyl groups) present on the surface of the metal oxide (A). For example, examples of such sites include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom. These halogen atoms and oxygen atoms can cause a condensation reaction (hydrolysis condensation reaction) with the hydroxyl groups existing on the surface of the metal oxide (A). A functional group (for example, a hydroxyl group) existing on the surface of the metal oxide (A) is usually bonded to a metal atom (M) constituting the metal oxide (A).

As the phosphorus compound (B), for example, a compound having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used, and by using such a phosphorus compound (B), a metal oxide (A) can be used. It can be bonded by (hydrolyzing) condensing with the hydroxyl group existing on the surface of. The phosphorus compound (B) may have one phosphorus atom or may have two or more phosphorus atoms.

The phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof. Specific examples of polyphosphoric acid include pyrophosphoric acid, triphosphate, and polyphosphoric acid in which four or more phosphoric acids are condensed. Examples of the above derivatives include salts of phosphoric acid, polyphosphoric acid, phosphorous acid, and phosphonic acid, (partial) ester compounds, halides (chlorides, etc.), dehydrated products (nilin pentoxide, etc.), and the like. .. Further, in the example of the derivative of phosphonic acid, _{the hydrogen atom directly bonded to the phosphorus atom of phosphonic acid (HP (= O) (OH) 2} ) may have various functional groups as an alkyl group. Substituted compounds (eg, nitrilotris (methylenephosphonic acid), N, N, N', N'-ethylenediaminetetrax (methylenephosphonic acid), etc.) and salts thereof, (partial) ester compounds, halides and dehydrations. Things are also included. Further, an organic polymer having a phosphorus atom such as phosphorylated starch can also be used as the phosphorus compound (B). These phosphorus compounds (B) may be used alone or in combination of two or more. Among these phosphorus compounds (B), the stability of the coating liquid (U) and the water vapor barrier property of the obtained barrier film are more excellent when the barrier layer is formed by using the coating liquid (U) described later. , Phosphoric acid is preferably used alone, or phosphoric acid and other phosphorus compounds are used in combination.

As described above, the barrier layer contains the reaction product (R), and the reaction product (R) is a reaction product formed by at least the reaction of the metal oxide (A) and the phosphorus compound (B). be. Such a reaction product can be formed by mixing and reacting the metal oxide (A) and the phosphorus compound (B). The phosphorus compound (B) to be mixed with the metal oxide (A) (immediately before being mixed) may be the phosphorus compound (B) itself, or the form of the composition containing the phosphorus compound (B). However, the form of the composition containing the phosphorus compound (B) is preferable. In a preferred example, the phosphorus compound (B) is mixed with the metal oxide (A) in the form of a solution obtained by dissolving the phosphorus compound (B) in a solvent. Any solvent can be used at that time, and water or a mixed solvent containing water can be mentioned as a preferable solvent.

In the composition containing the phosphorus compound (B) or the phosphorus compound (B) to be mixed with the metal oxide (A), the content of the metal atom is reduced due to the water vapor barrier property and its stability. It is preferable because an excellent barrier film can be obtained. The content of the metal atom contained in the phosphorus compound (B) or the composition containing the phosphorus compound (B) to be mixed with the metal oxide (A) is the phosphorus compound (B) or the phosphorus compound (B). Based on the number of moles of all phosphorus atoms contained in the composition containing (100 mol%), it is preferably 100 mol% or less, more preferably 30 mol% or less, and 5 mol% or less. More preferably, it is particularly preferably 1 mol% or less, and it may be 0 mol%.

(Reaction product (R))
The reaction product (R) includes a reaction product produced by the reaction of only the metal oxide (A) and the phosphorus compound (B). The reaction product (R) also includes a reaction product produced by the reaction of the metal oxide (A), the phosphorus compound (B), and another compound. The reaction product (R) can be formed by the method described in the production method described later.

(Ratio of metal oxide (A) and phosphorus compound (B))
In the barrier layer, a metal oxide molar number N _M and phosphorus compounds of the metal atoms constituting the (A) and the mole number N _P of phosphorus atoms derived from the (B) is, 1.0 ≦ (number of moles N _M) / it is preferable to satisfy the relation of (number of moles _{N P)} ≦ 3.6, more preferably satisfy the relation of 1.1 ≦ (number of moles _N M) / (number of moles _{N P)} ≦ 3.0. When _{the value of (number of moles NM} ) / (number of moles _NP ) exceeds 3.6, the metal oxide (A) becomes excessive with respect to the phosphorus compound (B), and the particles of the metal oxide (A) become mutual. In addition, the amount of hydroxyl groups present on the surface of the metal oxide (A) increases, so that the water vapor barrier property and its stability tend to decrease. On the other hand, when _{the value of (number of moles NM} ) / (number of moles _NP ) is less than 1.0, the phosphorus compound (B) becomes excessive with respect to the metal oxide (A), and the metal oxide (A) The excess phosphorus compound (B) that is not involved in the bond with the phosphorus compound (B) tends to increase, and the amount of hydroxyl groups derived from the phosphorus compound (B) tends to increase, and the water vapor barrier property and its stability also tend to decrease.

The above ratio can be adjusted by the ratio of the amount of the metal oxide (A) to the amount of the phosphorus compound (B) in the coating liquid for forming the barrier layer. The ratio of the moles N _M and the number of moles N _P in the barrier layer is usually composed moles of phosphorus compound of a metal atom constituting the metal oxide there the ratio in the coating solution (A) and (B) phosphorus It is the same as the ratio to the number of moles of atoms.

(Polymer (C))
The barrier layer may further contain the specific polymer (C). The polymer (C) is a polymer having at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of the carboxyl group. In the barrier layer, the polymer (C) is directly or indirectly with one or both of the particles of the metal oxide (A) and the phosphorus atom derived from the phosphorus compound (B) due to the functional group (f) it has. It may be combined. Further, in the barrier layer, the reaction product (R) may have a polymer (C) moiety formed by the reaction of the polymer (C) with the metal oxide (A) or the phosphorus compound (B). .. In addition, in this specification, a polymer which satisfies the requirement as a phosphorus compound (B) and contains a functional group (f) is treated as a phosphorus compound (B) without being included in the polymer (C). ..

As the polymer (C), a polymer containing a structural unit having a functional group (f) can be used. As a specific example of such a structural unit, a functional group (f) such as a vinyl alcohol unit, an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, an itaconic acid unit, a maleic anhydride unit, and a phthalic anhydride unit is set to 1. Examples thereof include structural units having one or more. The polymer (C) may contain only one type of structural unit having a functional group (f), or may contain two or more types of structural units having a functional group (f).

In order to obtain a barrier film having better water vapor barrier property and its stability, the ratio of the structural unit having the functional group (f) to the total structural unit of the polymer (C) is 10 mol% or more. It is preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

When the polymer (C) is composed of a structural unit having a functional group (f) and other structural units other than that, the type of the other structural unit is not particularly limited. Examples of such other building blocks are derived from (meth) acrylic acid esters such as methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units. Constituent units derived from vinyl esters such as vinyl formate units and vinyl acetate units; Constituent units derived from aromatic vinyl such as styrene units and p-styrene sulfonic acid units; Ethylene units, propylene units, And structural units derived from olefins such as isobutylene units are included. When the polymer (C) contains two or more kinds of structural units, the polymer (C) is any of an alternating copolymer, a random copolymer, a block copolymer, and a tapered copolymer. May be good.

Specific examples of the polymer (C) having a hydroxyl group include polyvinyl alcohol, a partially saponified product of polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, and polysaccharides derived from polysaccharides. Derivatives and the like can be mentioned. Specific examples of the polymer (C) having a carboxyl group, a carboxylic acid anhydride group, or a salt of a carboxyl group include polyacrylic acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), and salts thereof. Can be done. Specific examples of the polymer (C) containing a structural unit that does not contain the functional group (f) include an ethylene-vinyl alcohol copolymer, an ethylene-maleic anhydride copolymer, and a styrene-maleic anhydride copolymer. , Isobutylene-maleic anhydride copolymer, ethylene-acrylic acid copolymer, saponified product of ethylene-ethyl acrylate copolymer and the like. In order to obtain a barrier film having better water vapor barrier properties and its stability, the polymer (C) is a salt of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, polyacrylic acid. , Polymethacrylic acid, and at least one polymer selected from the group consisting of salts of polymethacrylic acid.

The molecular weight of the polymer (C) is not particularly limited. In order to obtain a barrier film having better water vapor barrier properties and mechanical properties (drop impact strength, etc.), the number average molecular weight of the polymer (C) is preferably 5,000 or more. It is more preferably 000 or more, and further preferably 10,000 or more. The upper limit of the number average molecular weight of the polymer (C) is not particularly limited, and is, for example, 1,500,000 or less.

In order to further improve the water vapor barrier property, the content of the polymer (C) in the barrier layer is preferably 50% by mass or less, preferably 40% by mass or less, based on the mass of the barrier layer (100% by mass). It is more preferably 30% by mass or less, and it may be 20% by mass or less. The polymer (C) may or may not react with other components in the barrier layer. In addition, in this specification, when a polymer (C) reacts with another component, it is also referred to as a polymer (C). For example, when the polymer (C) is bonded to a phosphorus atom derived from a metal oxide (A) and / or a phosphorus compound (B), it is also referred to as a polymer (C). In this case, the content of the polymer (C) is calculated by dividing the mass of the polymer (C) before binding to the metal oxide (A) and / or the phosphorus atom by the mass of the barrier layer.

The barrier layer is composed of at least a reaction product (R) formed by the reaction of a metal oxide (A) and a phosphorus compound (B) (including one having a polymer (C) moiety). It may be composed only of the reaction product (R) and the unreacted polymer (C), but may further contain other components.

Other components described above include, for example, inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogen carbonates, sulfates, hydrogen sulfates, borates, aluminates; oxalates, acetates, etc. Organic acid metal salts such as tartrate and stearate; metal complexes such as acetylacetonate metal complex (aluminum acetylacetonate etc.), cyclopentadienyl metal complex (titanosen etc.), cyanometal complex; layered clay compound; crosslinked Agents; polymer compounds other than the polymer (C); plasticizers; antioxidants; UV absorbers; flame retardants and the like.

The content of the other components in the barrier layer is preferably 50% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and 5% by mass or less. It is particularly preferable to have 0% by mass (not containing other components).

The thickness of the barrier layer (the total thickness of each barrier layer when having two or more barrier layers) is preferably 4.0 μm or less, more preferably 2.0 μm or less, and 1 It is more preferably 0.0 μm or less, and particularly preferably 0.9 μm or less. By making the barrier layer thinner, the dimensional change of the barrier film during processing such as printing and laminating can be suppressed to a low level, and the flexibility of the barrier film is further increased. It can be approached to the target characteristics. The thickness of the barrier layer can be controlled by the concentration of the coating liquid (U) used for forming the barrier layer, which will be described later, and the coating method thereof.

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

<Packaging material>
The barrier film according to the present invention can be 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.

<Manufacturing of barrier film>
[Example 1]
(Adjustment of coating liquid)
The temperature was raised to 70 ° C. with stirring 230 parts by mass of distilled water. 88 parts by mass of aluminum isopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the distilled water over 30 minutes, the liquid temperature was gradually raised to 95 ° C., and the generated isopropanol was distilled to add water. Decomposition and condensation were performed. To the obtained liquid, 4.0 parts by mass of a 60% by mass nitric acid aqueous solution was added, and the mixture was stirred at 95 ° C. for 30 minutes to dissolve the aggregates of the particles of the hydrolyzed condensate. It was concentrated to 10% by mass in terms of alumina. To 16.79 parts by mass of the dispersion liquid thus obtained, 30.89 parts by mass of distilled water, 19.00 parts by mass of methanol, and 0.61 parts by mass of a 4 mass% polyvinyl alcohol aqueous solution were added to make the mixture uniform. The dispersion liquid A was obtained by stirring the mixture. Further, 32.72 parts by mass of an aqueous phosphoric acid solution diluted to 8.5% by mass was used as the solution B. Subsequently, while stirring the dispersion liquid A, the solution B was added dropwise at room temperature (23 ° C.) to obtain a coating liquid C.

Next, 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 chemical vapor deposition film 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 conditions)
・ 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
Next, the coating liquid C is applied to the surface of the chemical vapor deposition film, dried at 120 ° C. for 5 minutes, and then heat-treated at 180 ° C. for 5 minutes to achieve the thickness of the coated film after drying. A barrier layer having a thickness of 0.3 μm was formed to obtain a barrier film.

[Example 2]
A barrier film was obtained in the same manner as in Example 1 except that the chemical vapor deposition film surface of Example 1 was surface-treated with plasma and then coated with the coating liquid C.
(Plasma processing conditions)
・ Input power 0.3kW
・ Gas composition O ₂
・ Gas flow rate 900 sccm
・ Chamber pressure 3Pa
・ Film transfer speed 2m / min

[Comparative Example 1]
A commercially available silica-deposited film (carbon ratio of less than 5% of silica-deposited) was prepared, and a barrier film was obtained in the same manner as in Example 1 except that the coating liquid C was applied to the silica-deposited surface of the film.

[Comparative Example 2]
A barrier film was obtained in the same manner as in Example 1 except that the chemical vapor deposition film 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 Tecnolox DELTA PARM. It was measured in the initial state, and after storage for 500 hours in an environment of a temperature of 60 ° C. and a humidity of 90%.

(Water resistance adhesion evaluation method)
The barrier layer surface of the barrier film and the nylon film were bonded together, and the unstretched polypropylene film was further bonded on the nylon film to prepare a laminated film for evaluating water resistance and adhesion having the following layer structure.
Layer structure: Barrier film / DL / ONY 15 μm / DL / CPP 60 μm
(DL: dry laminate, ONY: nylon film, CPP: unstretched polypropylene film)
Using the obtained laminated film, T-shaped peeling was performed while water was dripped on the peeling interface, and the water-resistant lami strength (N / 15 mm) was measured at a measurement speed of 50 mm / min and evaluated according to the following criteria.
[Evaluation criteria]
⊚: 2.5N / mm or more ○: 2 to 2.5N / 15mm
X: 2N / 15 mm or less

10 Barrier film 11 Resin base material 12 Intermediate layer 13 Barrier layer

Claims (8)

A barrier film having a resin base material, an intermediate layer, and a barrier layer in this order.
The intermediate layer is a thin-film film containing silicon, oxygen, and carbon, and the ratio C of carbon is 13 % or more and 23 % with respect to a total of 100% of the three elements of silicon, oxygen, and carbon in the thin-film film. Is below
The barrier layer is a coating layer containing a reaction product of a metal oxide and a phosphorus compound and at least one polymer selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers. Barrier film. The barrier film according to claim 1, wherein the resin base material is a polyolefin resin base material or a polyester resin base material. The barrier film according to claim 1 or 2, wherein the metal oxide is an aluminum oxide. The barrier according to any one of claims 1 to 3, wherein the phosphorus compound is at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof. Sex film. The barrier film according to any one of claims 1 to 4, wherein the vapor-deposited film is a chemical vapor deposition film. The barrier film according to any one of claims 1 to 5, wherein the water vapor transmission rate is 9.0 × 10 ^-2 g / m ^{2 / day or less.} Temperature 60 ° C. and 90% humidity for 500 hours water vapor transmission rate after storage in an environment is, 9.0 × is ¹⁰ -2 ^g / m 2 / day or less, according to any one of claims 1 to 5 Barrier film. The barrier film according to any one of claims 1 to 7, which is used as a packaging material.

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