JP2018058253A - Gas permeability control laminate and manufacturing method thereof - Google Patents

Abstract

The present invention provides a gas permeability control laminate that exhibits excellent gas permeability controllability over a long period of time in a humidity environment, and a method for manufacturing the same. A gas permeability control laminate 10 includes a resin base material 11, a vapor deposition layer 12 laminated on at least one side of the resin base material 11, and an overcoat layer 13 on the vapor deposition layer 12. A slit-like gap having a width of 2 to 50 nm is formed across both the vapor deposition layer 12 and the overcoat layer 13. By setting the slit-shaped gap to a mesopore size of 2 to 50 nm, in a high humidity atmosphere, the mesopore gap is filled with water vapor by capillary condensation, and other gases are blocked. When almost all the gaps are filled with water vapor, the barrier properties inherent to the laminate other than the gaps are exhibited, so that extremely high gas barrier properties are exhibited. On the other hand, since the gap is not filled with water vapor in a dry atmosphere, other gases can also permeate. [Selection] Figure 1

Description

  The present invention relates to a laminate having excellent barrier properties against a specific gas and having permeability controllability by a humidity atmosphere, and a laminate having selective permeability of any gas and water vapor, and a method for producing the laminate.

  The gas permeability control laminate is a laminate having a selective permeability of a specific gas such as hydrogen, oxygen, and water vapor, and the laminate capable of arbitrarily controlling the transmittance according to the measurement atmosphere. It is. For this reason, the member held in the portion shielded by the gas permeability control laminate can suppress deterioration / degeneration caused by external gas while discharging excess gas. In recent years, such gas permeability control laminates are expected to be used in various fields.

  For example, in packaging applications such as foods and pharmaceuticals, it is required to prevent the contents from being altered or deteriorated, and a laminate such as a gas barrier film is used. However, the selectivity of the gas to be permeated and discharged is often required. Specifically, in the secondary outer packaging of primary containers such as hydrated foods and medicines, excess water and generated gas released from the primary container are discharged, but proteins, oils, chemicals, etc. in the primary container are discharged. It is required to prevent the inflow of oxygen that causes oxidation and alteration. Furthermore, when these exterior bodies are replaced with an inert gas such as helium or argon, nitrogen, carbon dioxide, or the like, it is required to suppress a decrease in the replacement gas. For this reason, a gas control laminated body with high selective permeability is used.

  Further, such a gas permeability control laminate is expected to be used as a laminate used for packaging containers such as culture. Specifically, it is required to discharge unnecessary generated gas or adjust the moisture content without opening and closing while suppressing the alteration of the active ingredient in the contents. For this reason, there is a need for a gas permeability control laminate that can change and control the transmission characteristics arbitrarily by adjusting the humidity.

  Further, such a gas permeability control laminate is suitably used in a field where water vapor permeates but is required to prevent deterioration due to hydrogen or oxygen cross leak, such as an electrolyte protective film in a fuel cell. Yes.

When such a gas permeability control laminate is used as a packaging member, it is preferable to have transparency. Because the packaging material has transparency, the shape of the contents and the color of the contents can be visually confirmed from the outside of the package, which prevents the contents from being mixed and whether the contents are damaged or not. The presence or absence of alteration can be grasped before opening.

  As described above, the gas permeability control laminate has advanced characteristics such as transparency, moisture resistance, weather resistance, and durability in addition to gas permeability control so that it can be used in a wide variety of applications. It is required to have a level.

  Conventionally, a gas barrier laminate in which a gas barrier substance is vapor-deposited on a film substrate is known as a gas barrier laminate. The vapor deposited film of the gas barrier material has a gas barrier property and is also very thin because it is extremely thin.

Examples of such gas barrier laminates include silica-based vapor deposition films and alumina reaction vapor deposition films. Silica-vapor deposited film, the film substrate is a laminate formed by depositing silicon monoxide or Si / SiO ₂ mixed material. The alumina reactive vapor deposition film is a laminate that is vapor-deposited by reacting evaporated metal aluminum and oxygen on a film substrate.

  Here, since the silica-based vapor deposition film and the alumina reaction vapor deposition film have gas barrier properties that are easily affected by temperature and moisture, gas barrier laminates with improved heat resistance, water resistance, and moisture resistance have been proposed ( (See Patent Document 1 and Patent Document 2).

  The laminates disclosed in Patent Document 1 and Patent Document 2 are further provided with a water-soluble polymer such as polyvinyl alcohol and an alkoxysilane such as tetraethoxysilane or its hydrolysis on a vapor deposition film provided on a substrate. A coating solution containing the product is applied and dried by heating to provide a gas barrier film. With such a configuration, gas barrier properties, heat resistance, water resistance, moisture resistance, and the like are improved.

  In Patent Document 3, an ethylene-vinyl alcohol copolymer is used to improve the relative selective permeability of carbon dioxide gas to oxygen gas.

Japanese Patent Laid-Open No. 7-164591 International Publication No. 2004/048081 JP-A-63-41539

  However, the gas barrier laminates described in Patent Documents 1 and 2 block many types of gases such as oxygen, water vapor, and carbon dioxide gas, and thus selective permeability cannot be expected. Moreover, it is known that the ethylene-vinyl alcohol copolymer as disclosed in Patent Document 3 has high gas permeability as a whole in a high humidity atmosphere, and the gas barrier function is significantly reduced.

  Gas barrier laminates are required not only to shut off gas, but also to have a permeability control mechanism such as selective permeability and permeation gas adjustment according to the in-situ atmosphere as the use of the gas barrier laminate increases. However, a laminate having a high water vapor permeability while having a high gas barrier function in a high humidity atmosphere is not known.

  The present invention has been made in view of the above circumstances, and provides a gas permeability control laminate that exhibits excellent gas permeability controllability over a long period of time in a humidity environment, and a method for manufacturing the same. Objective.

  As a result of intensive studies, the inventor has found that specific gas permeability is controlled in the gas barrier laminate, and has completed the present invention. The present invention has, for example, the following aspects.

  The gas permeability control laminate according to the present invention includes a resin base material and a vapor deposition layer laminated on at least one side of the resin base material, and has a slit-like gap having a width of 2 to 50 nm in the vapor deposition layer. It is what.

  An overcoat layer may be further provided on the vapor deposition layer, and a slit-like gap having a width of 2 to 50 nm may be provided over the vapor deposition layer or both the vapor deposition layer and the overcoat layer.

  Moreover, it is preferable that the pitch of a slit-shaped gap is 0.1 μm to 10 mm.

  Moreover, the measurement conditions of a laminated body are 40 degreeC, 0% R. H. Helium permeability dryHeTR and measurement conditions of 40 ° C., 90% R.V. H. It is preferable that the ratio d / w to the helium permeability wetHeTR at 5 is 5 or more.

  An anchor coat layer may be further provided between the resin substrate and the vapor deposition layer.

  A laminate resin layer may be further laminated on the overcoat layer via an adhesive layer.

  The method for producing a gas permeability control laminate according to the present invention includes a step of forming a laminate in which a vapor deposition layer is laminated on at least one side of a resin base material, and a crack is applied by applying a tensile load in at least one direction to the laminate. Generating a slit-shaped gap having a width of 2 to 50 nm in the vapor deposition layer.

  A step of laminating an overcoat layer on the vapor deposition layer may be provided, and in the step of forming the slit gap, the slit gap may be formed over both the vapor deposition layer and the overcoat layer.

  You may provide the process of forming an anchor coat layer further between a resin base material and a vapor deposition layer.

  A step of laminating a laminate resin layer on the overcoat layer via an adhesive layer may be further provided.

  The gas permeability laminate of the present invention is a laminate capable of easily controlling the permeability of gases other than water vapor in a humidity atmosphere. The gas-permeability laminate of the present invention has a specific permeation characteristic that a high gas barrier property can be expressed at high humidity while water vapor permeability is high, particularly for a specific gas. By these characteristics, even in a harsh environment, deterioration of the overcoat layer and the vapor deposition layer is suppressed, and excellent gas permeation controllability is exhibited over a long period of time. Therefore, according to the present invention, it is possible to provide a gas permeability control laminate that can be used for various specific applications and that exhibits excellent gas permeability controllability over a long period of time.

Schematic sectional view of a gas permeability control laminate according to an embodiment of the present invention Schematic sectional view of a gas permeability control laminate according to an embodiment of the present invention Schematic sectional view of a gas permeability control laminate according to an embodiment of the present invention

  Hereinafter, an embodiment of a gas permeability control laminate according to an embodiment of the present invention will be specifically described with reference to the drawings. However, the specific configuration of the present invention is not limited to the contents of the following embodiment, and even if there is a design change or the like within a range not departing from the gist of the present specification, they are included in the present invention.

  The gas permeability control laminate of this embodiment is a laminate comprising a resin substrate, a vapor deposition layer laminated on at least one side of the resin substrate, and an overcoat layer on the vapor deposition layer, It has a slit-like gap with a width of 2 to 50 nm in the vapor deposition layer or over both the vapor deposition layer and the overcoat layer.

  Surfaces other than the slit-shaped gap have excellent barrier properties, and the permeability can be adjusted by forming the slit-shaped gap.

  In particular, by setting the gap to a mesopore size of 2 to 50 nm, in a high humidity atmosphere, the mesopore gap is filled with water vapor by capillary condensation, and other gases are blocked. When almost all the gaps are filled with water vapor, the barrier properties inherent to the laminate other than the gaps are exhibited, so that extremely high gas barrier properties are exhibited.

  On the other hand, since the gap is not filled with water vapor in a dry atmosphere, other gases can also permeate. Thus, the gas permeability control laminate of this embodiment is also a laminate capable of controlling permeability with humidity.

In particular, if the permeation of helium gas can be controlled, other gases such as hydrogen, oxygen, and CO _{2 having a} molecular size larger than that of helium can be simultaneously shielded and permeated. Therefore, the gas permeation control laminate of the present invention can control the path structure through which helium can pass through humidity while having high water vapor permeability, so that it has unique permeation characteristics and excellent durability and the like. It can be set as a laminated body.

(Gas permeability control laminate)
FIG. 1 shows a schematic cross-sectional view of a gas permeability control laminate according to an embodiment of the present invention. The gas permeability control laminate 10 is a laminate having a structure in which a vapor deposition layer 12 and an overcoat layer 13 are sequentially laminated on one surface of a resin base material 11, and has a slit-like gap 14. Hereinafter, on the basis of the resin base material 11, the direction in which the vapor deposition layer 12 and the overcoat layer 13 are laminated will be described as the top (layer).

<Resin substrate>
The resin base material 11 is a layer that becomes a base of the gas permeability control laminate 10. The resin base material 11 may be appropriately selected from various sheet-like base materials (including film-like materials) that are generally used. For example, (1) Polyester film such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), (2) Polyolefin film such as polyethylene and polypropylene, (3) Polyether sulfone (PES), polystyrene film, polyamide film, poly Examples thereof include a vinyl chloride film, a polycarbonate film, a polyacrylonitrile film, a polyimide film, and a biodegradable plastic film such as polylactic acid.

  The resin substrate 11 may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant.

  In addition, the thickness of the resin base material 11 is not particularly limited, and may be appropriately determined according to specifications. Practically, the thickness of the resin substrate is desirably about 6 μm to 200 μm, preferably about 12 μm to 125 μm, and more preferably about 12 μm to 50 μm. However, in the gas permeability control laminated body 10 of this embodiment, the thickness of the resin base material 11 is not limited to the said range.

  Moreover, you may surface-treat to the resin base material 11 surface. By performing the surface treatment, the adhesion to the resin base material 11 can be enhanced in stacking other layers (evaporation layer, anchor coat layer, etc.). Here, as the surface treatment, for example, (1) physical treatment such as corona treatment, plasma treatment, flame treatment, or (2) chemical treatment such as chemical treatment with acid or alkali may be used.

<Deposition layer>
The vapor deposition layer 12 is a layer formed in an upper layer than the resin base material 11 by vapor-depositing vapor deposition material in order to provide gas barrier property. The vapor deposition material used for the vapor deposition layer 12 may be appropriately selected from inorganic materials constituting a known gas barrier vapor deposition film. Examples thereof include metals such as Si, Al, Zn, Sn, Fe, and Mn, and inorganic compounds containing one or more of these metals. Examples of the inorganic compound include oxides, nitrides, carbides, fluorides, and the like. Among these, at least one selected from metals and metal oxides is preferable. Specifically, silicon oxide (SiOx), such as silicon monoxide and silicon dioxide, aluminum oxide, magnesium oxide, tin oxide, etc. are mentioned, for example. Especially, the vapor deposition film containing an aluminum oxide is excellent in helium barrier property, and is suitable.

  The vapor deposition layer 12 is particularly preferably formed by vacuum vapor deposition using a vapor deposition material containing metallic aluminum and reacting while introducing oxygen. The vapor deposition layer 12 formed as described above is particularly excellent in transparency and barrier properties against oxygen gas and water vapor. In the vapor deposition material, the content ratio of aluminum and oxygen is preferably such that the element ratio O / Al between aluminum and oxygen is 1.0 or more and 2.0 or less, and O / Al is 1.4 or more. The ratio is more preferably 2.0 or less. When O / Al is 1.4 or more, the transparency is good, and when O / Al is 2.0 or less, the barrier property is good. Furthermore, when O / Al is 2.0 or less, a dense film is formed, which is suitable for helium barrier properties.

  A method for forming the vapor deposition layer 12 may be appropriately selected from known vapor deposition methods. For example, a physical vapor deposition (PVD) method such as a vacuum deposition method or a sputtering method, a chemical vapor deposition (CVD) method such as an ion plating method or a plasma vapor deposition method, or ALD: An atomic layer deposition method or the like may be used. In particular, the vacuum deposition method using EB (electron beam heating) can obtain a high film formation rate, and is preferable as a method for forming the vapor deposition layer 12 of the gas barrier laminate of the present embodiment.

Moreover, you may use the reactive vapor deposition method in performing vapor deposition. The reactive vapor deposition method is a method in which vapor deposition is performed by reacting evaporated particles with a gas introduced into the atmosphere when vapor deposition is performed. Examples of the gas to be introduced include oxygen gas and argon gas. By performing reactive vapor deposition with oxygen gas or the like, the metal component in the vapor deposition material is oxidized, and the transparency of the vapor deposition layer 12 can be improved. In addition, when the reactive vapor deposition method is used, it is desirable that the pressure of the film formation chamber when introducing the gas is 2 × 10 ⁻¹ Pa or less. If the pressure in the film forming chamber is higher than 2 × 10 ⁻¹ Pa, the vapor deposition layer 12 may not be neatly laminated, and the water vapor barrier property may be deteriorated.

  The film thickness of the vapor deposition layer 12 is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm. When the thickness is 5 nm or more, sufficient barrier properties are exhibited, and when the thickness is 300 nm or less, generation of cracks in the post-process and the like, and deterioration of the barrier properties are less likely to occur. However, in the gas barrier laminate 10 of the present embodiment, the film thickness of the vapor deposition layer 12 is not limited to the above range.

<Overcoat layer>
The overcoat layer 13 is a layer formed on the vapor deposition layer 12. By laminating the overcoat layer 13 on the vapor deposition layer 12, it is possible to obtain an excellent gas barrier property that cannot be expressed in a gas permeability control laminated body in which the vapor deposition layer 12 is composed of a single layer. The overcoat layer also has a function of protecting the dense and fragile deposited layer 12 and can suppress the occurrence of cracks due to rubbing or bending. The overcoat layer 13 is formed by adjusting the coating solution, applying the coating solution on the vapor deposition layer 12, and heating and drying the coating solution.

The overcoat layer 13 includes a component containing a silicon compound (A) having a siloxane bond, a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, and an acrylic polyol containing a hydroxyl group and a carboxyl group. It is preferable that the inorganic component content ratio in the overcoat layer is 55 wt% or more and 90 wt% or less in terms of SiO ₂ .

  Contains any one of a silicon compound (A) having a siloxane bond, a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, and an acrylic polyol containing a hydroxyl group and a carboxyl group (B) The coating liquid to be formed is applied on the vapor deposition layer 12 and dried.

  The silicon compound (A) having a siloxane bond is a hydrolysis product of an organosilicon compound such as an alkoxysilane or a silane coupling agent. The alkoxysilane is dissolved in an alcohol such as methanol, and an acid such as hydrochloric acid is dissolved in the solution. What prepared by adding aqueous solution and making it hydrolyze is mentioned.

  As the alkoxysilane, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, methyltriethoxysilane, methyltrimethoxysilane, or the like can be used. Examples of organosilicon compounds such as silane coupling agents include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxy. Examples thereof include those having a mercapto group such as silane and those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more. These organosilicon compounds are preferable because they can form a coating film composed of an organic component and an inorganic component alone.

  The water-soluble polymer forming the overcoat layer of the present invention includes polyvinyl alcohol resin (PVA), polyacrylic acid resin (PAA), ethylene-vinyl alcohol copolymer resin (EVOH), and polyvinylpyrrolidone resin (PVP). Alternatively, an acrylic polyol having a hydroxyl group and a carboxyl group can be used, and these may be used alone or in combination.

The overcoat layer of the present invention is preferable because the content ratio of the inorganic component in the entire overcoat layer is 55 wt% or more in terms of SiO ₂ , so that excellent properties in barrier properties in a wet state can be obtained. is there. On the other hand, if the inorganic component exceeds 90%, sufficient barrier performance cannot be obtained, and the flexibility is remarkably lowered, which is not suitable.

  In order to improve the adhesion to the vapor deposition layer 12, an isocyanate compound having at least two isocyanate groups in the molecule may be added.

  As a coating method of the coating solution, a normal coating method can be used. For example, a known method such as a dipping method, a low coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, or a gravure offset method can be used. As a drying method, one or a combination of two or more methods of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, can be used. In the drying method, the heating temperature is preferably in the range of about 60 ° C. to 200 ° C., more preferably in the range of about 100 ° C. to 150 ° C. When it is 60 ° C. or higher, desired barrier properties are exhibited, which is good. When it is 150 ° C. or lower, it is suitable without causing deformation of the base material or film damage.

  The film thickness of the overcoat layer 13 is preferably about 0.1 μm to 2 μm, and more preferably about 0.2 μm to 1.0 μm. When it is 0.2 μm or more, the barrier property is stably expressed, and when it is 1 μm or less, it is excellent in post-processing suitability such as printing or lamination of other films or bending. However, in the gas barrier laminate 10 of the present embodiment, the film thickness 13 of the overcoat layer is not limited to the above range.

  Further, the gas permeability control laminate 10 of the present embodiment may be plate-shaped or film-shaped. For example, it may be formed into a film shape by winding with a roll or the like.

<Anchor coat layer>
Moreover, the gas barrier laminate 10 of this embodiment may further include an anchor coat layer 24 between the resin base material 11 and the vapor deposition layer 13. By providing the anchor coat layer 24, the adhesion between the resin base material 11 and the vapor deposition layer 12 can be improved, and the occurrence of peeling between the layers can be suppressed. The anchor coat layer 24 is a layer serving as a base for the vapor deposition layer 12 in particular, and has a great influence on the number of defects of the vapor deposition layer 12, has high thermal stability, has few foreign matters, and is preferably in a smooth and homogeneous state. Due to the underlying effect of the vapor deposition layer 12, the number of defects in the vapor deposition layer 12 can be reduced, the helium permeability is reduced, and the barrier property against oxygen and water vapor is also suitable.

  FIG. 2 shows a schematic cross-sectional view of the gas barrier laminate 20 in which the anchor coat layer 24 is laminated. The gas permeability control laminate 20 is a laminate having a structure in which the anchor coat layer 24, the vapor deposition layer 12, and the overcoat layer 13 are sequentially laminated on one surface of the resin base material 11.

  The anchor coat layer 24 is formed by adjusting the anchor coat agent, applying the anchor coat agent on the resin substrate 11, and heating and drying the applied anchor coat agent. The anchor coating agent preferably contains an acrylic polyol (1) having two or more OH groups and an isocyanate compound (2) having at least two NCO groups in the molecule.

  As the acrylic polyol (1), a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having an OH group and another monomer are copolymerized. Examples thereof include a polymer compound obtained. Examples of the (meth) acrylic acid derivative monomer having an OH group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate. As the other monomer copolymerizable with the (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having no OH group is preferable. Examples of (meth) acrylic acid derivative monomers having no OH group include (meth) acrylic acid derivative monomers having an alkyl group, (meth) acrylic acid derivative monomers having a carboxyl group, and (meth) acrylic having a ring structure. Examples include acid derivative monomers. Examples of (meth) acrylic acid derivative monomers having an alkyl group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. Is mentioned. Examples of the (meth) acrylic acid derivative monomer having a carboxyl group include (meth) acrylic acid. Examples of the (meth) acrylic acid derivative monomer having a ring structure include benzyl (meth) acrylate and cyclohexyl (meth) acrylate. As other monomers, monomers other than (meth) acrylic acid derivative monomers may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer. Monomers other than the (meth) acrylic acid derivative monomer may have an OH group.

  Moreover, it is preferable that OH group value of acrylic polyol (1) is 50 [mgKOH / g] or more and 250 [mgKOH / g] or less. The OH group value [mgKOH / g] is an index of the amount of OH groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide necessary for acetylating the hydroxyl group in 1 g of the acrylic polyol. When the OH group value is less than 50 [mgKOH / g], the amount of reaction with the isocyanate compound (2) is small, and the effect of improving the adhesion between the resin substrate 11 and the vapor deposition layer 12 by the anchor coat layer 24 is sufficient. May not develop. On the other hand, if the OH group value is larger than 250 [mgKOH / g], the amount of reaction with the isocyanate compound (2) increases so that the film shrinkage of the anchor coat layer 24 may increase. If the film shrinkage is large, the deposited layer 12 is not neatly laminated thereon, and there is a possibility that sufficient gas barrier properties are not exhibited.

  The weight average molecular weight of the acrylic polyol (1) is not particularly defined, but is preferably 3000 or more and 200000 or less, more preferably 5000 or more and 100000 or less, and further preferably 5000 or more and 40000 or less. In this specification, the weight average molecular weight is a weight average molecular weight measured by GPC (gel permeation chromatography) based on polystyrene. Moreover, acrylic polyol (1) may be used individually by 1 type, or may use 2 or more types together.

  The isocyanate compound (2) may be any compound having at least two NCO groups in the molecule. For example, monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate. Aliphatic isocyanates such as (H12MDI), aromatic aliphatic isocyanates such as xylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI) may be used. Further, polymers or derivatives of these monomeric isocyanates may also be used. Examples of the polymer or derivative include a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret, and the like. As an isocyanate compound (2), you may select arbitrarily from said monomeric isocyanate, its polymer, a derivative, etc., and can be used individually by 1 type or in combination of 2 or more types.

  In the anchor coating agent, the equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound (2) to the OH group of the acrylic polyol (1) is preferably 0.3 or more and 2.5 or less, More preferably, it is 2.0 or less. When NCO / OH is 0.3 or more, the adhesion to the substrate is improved, and when it is 2.0 or less, the adhesion after the wet heat resistance test is improved. The blending amount of the acrylic polyol (1) and the isocyanate compound (2) in the anchor coating agent is preferably blended based on the equivalent ratio, and the isocyanate compound (2) is generally based on 100 parts by mass of the acrylic polyol (1). The amount is preferably about 10 parts by mass or more and 90 parts by mass or less, and more preferably about 20 parts by mass or more and 80 parts by mass or less.

  The anchor coating agent may further contain a silane coupling agent in order to further improve the adhesion between the resin base material and the vapor deposition layer. Examples of the silane coupling agent include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. Examples thereof include those having a mercapto group and those having an isocyanate group such as 3-isocyanatopropyltriethoxysilane. Moreover, as a silane coupling agent, 1 type may be used independently or 2 or more types may be used together.

  The anchor coating agent can be prepared by mixing an acrylic polyol (1), an isocyanate compound (2), an optional component (such as a silane coupling agent), and a solvent. Any solvent may be used as long as it can dissolve the acrylic polyol (1) and the isocyanate compound (2). Examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, and acetone. These solvents can be used alone or in combination of two or more.

  As a method for applying the anchor coating agent, a normal coating method can be used. For example, known methods such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, and a gravure offset method can be used. As a drying method, one or a combination of two or more methods of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, can be used. In the drying method, the heating temperature is not particularly limited, but is preferably in the range of about 60 ° C. or more and 140 ° C. or less, so-called blocking phenomenon in which the coated surface sticks to the back surface even if winding processing is performed so that there is no residual solvent. The aging treatment may be performed within a range of about 40 ° C. to 60 ° C. as necessary.

  The film thickness of the anchor coat layer 24 is preferably 0.02 μm or more and 1.0 μm or less, and more preferably 0.04 μm or more and 0.5 μm or less. Adhesiveness of the resin base material 11 and the vapor deposition layer 12 becomes fully favorable as it is 0.02 micrometer or more. If it is thicker than 0.5 μm, the influence of internal stress becomes large, and the vapor deposition layer 12 is not neatly laminated, and there is a risk that the expression of gas barrier properties will be insufficient.

<Multilayer laminate>
Further, the gas permeability control laminated body 20 may have a multilayer structure in which at least one set of the vapor deposition layer 12 and the overcoat layer 13 are further laminated on the overcoat layer 13. By having one or more sets of multilayer structures, the barrier property is further improved, the effect of greatly reducing the gas permeability is high, and the overcoat layer 13 maintains long-term durability.

<Laminated resin layer>
Further, the gas permeability control laminated body 20 may further include a laminate resin layer 32 laminated via an adhesive layer 31 and the outermost surface may be the laminate resin layer 32. By providing the laminate resin layer 32 on the outermost surface, it is possible to impart functions and characteristics according to the application and enhance the practicality. Here, the laminate resin layer 32 may be formed only on one side or on both sides.

  In FIG. 3, the schematic sectional drawing of the gas-permeation-control laminated body 30 provided with the laminate resin layer 32 on both surfaces is shown. In the gas permeability control laminate 30, an anchor coat layer 24, a vapor deposition layer 12, an overcoat layer 13, an adhesive layer 31, and a laminate resin layer 32 are sequentially laminated on one surface of the resin substrate 11, and the resin substrate 11 This is a laminate in which an adhesive layer 33 and a laminate resin layer 34 are sequentially laminated on the other surface.

  The materials of the laminate resin layers 32 and 34 may be appropriately selected from known materials according to desired functions and characteristics. For example, by using a sealant film made of a heat-sealable resin for the laminate resin layers 32 and 24, the gas barrier laminate 30 can be used as an adhesive part when forming a bag-like package or the like. Can do. Examples of the resin constituting the sealant film include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene- Examples thereof include acrylic acid ester copolymers and their metal cross-linked products. The thickness of the sealant film is determined according to the purpose, but is generally in the range of 15 μm to 200 μm. In addition, when laminating the laminated resin layers 32 and 34 on both surfaces, it is good also as a structure which used the sealant film for any one and used resin films other than a sealant film for the other.

  For example, by using a polyethylene terephthalate film or a polyethylene naphthalate film for the laminate resin layers 32 and 34, a transparent conductive sheet used in a liquid crystal display element, a solar cell, an electromagnetic wave shield, a touch panel, etc. It can also be used as a sealing material. The formation of the laminate resin layers 32 and 34 may be appropriately performed using a known bonding method depending on the material of the selected laminate resin layers 32 and 34. For example, a laminating method such as dry lamination using an adhesive or extrusion molding using a heat-adhesive resin may be used. In the case of dry lamination using an adhesive, the adhesive forms an adhesive layer. Further, in the case of extrusion molding using a heat-adhesive resin, the heat-adhesive resin is configured to form the adhesive layer 31.

<Slit gap>
The slit-shaped gap 14 is formed in the vapor deposition layer of the gas permeation control laminate of the present invention or over both the vapor deposition layer and the overcoat layer, and the size (width) of the gap is a capillary phenomenon of water vapor. It is desirable that the thickness is 2 to 50 nm, which can be condensed by the above. If the size (width) of the slit-shaped gap is less than 2 nm or more than 50 nm, it is unsuitable because filling due to condensation is not observed.
The slit-shaped gap may be either continuous or discontinuous intermittently, and the pitch between the gaps is preferably 0.1 μm to 10 mm. If the thickness is less than 0.1 μm, the number of gaps increases, the strength of the film tends to decrease, and it is not preferable in view of stability over time. Also, if the gap between the gaps is larger than 10 mm, the difference in transmittance between the dry atmosphere and the humidity atmosphere is small, the adjustment range of the transmittance due to humidity is small, and a merit such as selective permeability cannot be expected.

  The method for producing the slit-shaped gap is not particularly limited, such as a method of forming a slit-shaped mask during vapor deposition and forming a film in a pattern, or an etching method by lithography.

  In particular, a method is provided by generating a crack-like gap by applying a tensile load in at least one direction to a laminate in which a vapor deposition layer is formed, or a laminate in which an overcoat layer is formed on the vapor deposition layer. Easy and desirable. The tensile load is not particularly limited, and the resin substrate itself of the laminate may be plastically deformed or elastically deformed. These tensile stretching processes are particularly problematic even when cold-stretched at about room temperature, when overcoating, at a temperature slightly higher than the Tg of the resin substrate at about 100 to 150 ° C., and at the same time as coating. Absent.

  Hereinafter, examples of the gas permeability control laminate of the present invention will be described in detail. However, the gas permeation control laminate of the present invention is not limited to the mode shown in the examples. The “solid content” indicating the content of the organosilicon compound or its hydrolyzate in the coating liquid for forming the overcoat layer and the anchor coat agent is a coating film formed by polymerization of the hydrolyzed organosilicon compound. The amount converted to weight.

The helium gas permeability was measured using a differential pressure type gas permeability measuring apparatus GTR-30XT manufactured by Yanaco. Helium gas permeability in H [cc / m ² · day · atm]: Humidity adjustment of dry-HeTR and test gas with a temperature-controlled bubbling bottle, 40 ° C. and 90% R.D. Helium gas permeability [cc / m ² · day · atm] under humidified conditions in H: Wet-HeTR was measured to obtain a transmittance ratio d / w-HeTR between a dry state and a wet state.

The oxygen permeability was measured using an oxygen permeability measuring device (OXTRAN-2 / 20 manufactured by Modern Control) in an atmosphere at 30 ° C. and a relative humidity of 70%. The measurement of water vapor transmission rate is performed using a water vapor transmission meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control Co., Ltd. under a 40 ° C.-90% RH atmosphere [g / m ² · day]. Was measured.

Example 1
First, the vapor deposition layer 12 was formed on the resin base material 11. As the resin base material 11, a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, P60) having a corona treatment on one side was used. Further, using a vacuum vapor deposition machine, the metal aluminum is evaporated while introducing oxygen so that the element ratio O / Al is 1.7 directly on the corona-treated surface of the resin base material 11. A vapor deposition layer 12 was formed on the material. At this time, the formed vapor deposition layer (AlOx vapor deposition film) was 18 nm in thickness.

Next, a coating solution for forming an overcoat layer was prepared. As an overcoat coating solution, a hydrolysis solution of tetraethoxysilane (TEOS) (added 5 times molar equivalent of tetraethoxysilane as water using 0.01N hydrochloric acid) and an aqueous solution of polyvinyl alcohol were used. A solution having a solid content of 5% by mass was prepared by mixing so that the mass ratio of the SiO ₂ equivalent amount to PVA was 60:40.

  Next, a coating solution was applied onto the vapor deposition layer 12 and dried by heating to form an overcoat layer 13. A bar coat was used for coating the coating solution. Moreover, the conditions of heat drying were 120 degreeC and 2 minutes. At this time, the dry film thickness of the formed overcoat layer 13 was 0.3 μm.

  Next, a tensile load was applied to this laminate using a tensile tester so that the elongation was 4%. After maintaining for 2 minutes, the load was removed and cracked gaps were formed in the vapor deposition layer and the overcoat layer. Was generated. The plastic deformation rate after the tensile test was about 0.5%.

The laminate was measured for the transmittance of helium gas. As a result, it was 2800 cc / (m ² · day · atm) at 40 ° C. and 0% RH, and 90 ° R. at 40 ° C. H. Then, it was 65 cc / (m ² · day · atm). From this, it was estimated that water vapor was condensed (filled) in the gap in a high humidity atmosphere, and the size of the gap was a nanopore size of 2 to 50 nm.

  From the above, the gas permeation control laminate of Example 1 in which the resin base material 11 / deposition layer 12 / overcoat layer 13 were laminated in this order was produced. In the gas barrier laminate of Example 1, the thickness of each layer was resin base material 11: 25 μm / deposition layer 12: 18 nm / overcoat layer 13: 0.3 μm.

[Inspection measurement]
The gas transmission control laminate of Example 1 was measured for oxygen transmission rate (O ₂ TR) and water vapor transmission rate (WVTR). O ₂ TR was 0.2 cc / (m ² · day · atm), and WVTR was 17 g / (m ² · day). The measurement results are shown in Table 1.

(Example 2)
First, an anchor coating agent was prepared. As an anchor coating agent, an acrylic polyol (weight average molecular weight of about 10,000) is prepared by copolymerizing hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) as monomers so that the OH group value is 178 mgKOH / g. A methyl ethyl ketone solution having a solid content of 5% by mass was prepared by blending hexamethylene diisocyanate (HDI) as a curing agent with the acrylic polyol as a main agent so as to be 0.5 equivalent to the amount of OH groups of the main agent.

  Next, an anchor coat agent was applied on the resin substrate 11 to form an anchor coat layer 24. As the resin base material 11, a 12 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, P60) having a corona treatment on one side was used. Using a gravure coater, the anchor coat agent was applied to the corona-treated surface of the resin substrate and stored in an oven at 50 ° C. for 48 hours (aging treatment) to form an anchor coat layer. At this time, the dry film thickness of the anchor coat layer 24 was 0.15 μm.

  Next, the vapor deposition layer 12 was formed on the anchor coat layer 24 in the same manner as in Example 1. Using a vacuum vapor deposition machine, metal aluminum was evaporated while oxygen was introduced so that the element ratio O / Al was 1.7, and a vapor deposition layer 12 was formed on the resin substrate. At this time, the formed vapor deposition layer (AlOx vapor deposition film) was 15 nm in thickness.

  Next, a coating solution for forming an overcoat layer was prepared. 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate hydrolysis solution as an overcoat coating solution (added 6 times molar equivalent of silylisocyanurate as water using 0.001N hydrochloric acid) Then, tetraethoxysilane was mixed so that silyl isocyanurate: tetraethoxysilane = 20: 80 (molar ratio), and diluted with IPA to prepare a solution having a solid content of 5% by mass.

  Next, a coating solution was applied onto the vapor deposition layer 12 and dried by heating to form an overcoat layer 13. A bar coat was used for coating the coating solution. The heating and drying conditions were 120 ° C. and 2 minutes. At this time, the dry film thickness of the formed overcoat layer was 0.5 μm.

  Next, using a tensile tester, a tensile load was applied to the laminate so that the elongation was 4%, and after maintaining for 2 minutes, the load was removed, and cracked gaps were formed in the vapor deposition layer and the overcoat layer. Generated. The plastic deformation rate after the tensile test was about 0.5%.

The laminate was measured for the transmittance of helium gas. As a result, it was 3200 cc / (m ² · day · atm) at 40 ° C. and 0% RH, and 90 ° R. at 40 ° C. H. Then, it was 180 cc / (m ² · day · atm). From this, it was estimated that water vapor was condensed in the gap under a high humidity atmosphere, and the size of the gap was a nanopore size of 2 to 50 nm.

  From the above, a gas barrier laminate of this example in which the resin base material 11 / anchor coat layer 24 / deposition layer 12 / overcoat layer 13 were laminated in this order was produced. In the gas barrier laminate 20 of this example, the film thickness of each layer was resin base material 11: 25 μm / anchor coat layer 24: 0.15 μm / deposition layer 12: 15 nm / overcoat layer 13: 0.5 μm. .

[Inspection measurement]
The gas barrier laminate obtained in Example 2 was subjected to various gas permeability measurements in the same manner as in Example 1. As a result, O ₂ TR was 0.3 cc / (m ² · day · atm), and WVTR was 28 g / (m ² · day). The measurement results are shown in Table 1.

(Example 3)
In the same manner as in Example 2, an anchor coat agent was applied on the resin substrate 11 to form an anchor coat layer 24. Next, using a vacuum vapor deposition machine, a vapor deposition material in which metal silicon powder and silicon dioxide powder are mixed so that the element ratio O / Si is 1.5 is vapor-deposited on the anchor coat layer. The vapor deposition layer 12 was formed in this. At this time, the formed vapor deposition layer (SiOx vapor deposition film) was 50 nm in thickness.

Next, a coating solution for forming an overcoat layer was prepared. As an overcoat coating solution, a hydrolysis solution of tetraethoxysilane (TEOS) (added 5 times molar equivalent of tetraethoxysilane as water using 0.01N hydrochloric acid) and an aqueous solution of polyvinyl alcohol were used. A solution having a solid content of 5% by mass was prepared by mixing so that the mass ratio of the SiO ₂ equivalent amount to PVA was 70:30.

  Next, a coating solution was applied onto the vapor deposition layer 12 and dried by heating to form an overcoat layer 13. A bar coat was used for coating the coating solution. Moreover, the conditions of heat drying were 120 degreeC and 2 minutes. At this time, the dry film thickness of the formed overcoat layer 13 was 0.3 μm.

Next, using a tensile tester, a tensile load was applied to the laminate so that the elongation was 4%, and after maintaining for 2 minutes, the load was removed, and cracked gaps were formed in the vapor deposition layer and the overcoat layer. The plastic deformation rate after the generated tensile test was about 0.5%.

When this laminate was measured for the transmittance of helium gas, it was 1980 cc / (m ² · day · atm) at 40 ° C. and 0% RH, and 40 ° C. and 90% R.H. H. Then, it was 340 cc / (m ² · day · atm). From this, it was estimated that water vapor was condensed in the gap under a high humidity atmosphere, and the size of the gap was a nanopore size of 2 to 50 nm.

  From the above, the gas barrier laminate of Example 3 in which the resin base material 11 / deposition layer 12 / overcoat layer 13 were laminated in this order was produced. In the gas barrier laminate of Example 1, the thickness of each layer was resin base material 11: 12 μm / deposition layer 12: 50 nm / overcoat layer 13: 0.3 μm.

[Inspection measurement]
The gas barrier laminate obtained in Example 3 was subjected to various gas permeability measurements in the same manner as in Example 1. As a result, O ₂ TR was 0.2 cc / (m ² · day · atm), and WVTR was 26 g / (m ² · day). The measurement results are shown in Table 1.

(Comparative Example 1)
As in Example 2, except that a biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, P60) having a thickness of 12 μm and subjected to corona treatment on one side is used as the resin base material 11 and the overcoat layer 13 is not provided. An anchor coat layer and a vapor deposition layer were provided, and a gas barrier laminate of Comparative Example 1 was produced in which resin base material 11 / anchor coat layer 24 / vapor deposition layer 12 were laminated in this order. In the gas barrier laminate of Comparative Example 1, the film thickness of each layer was resin base material 11:12 μm / anchor coat layer 24: 0.15 μm / deposition layer 12:15 nm.

[Inspection measurement]
The gas barrier laminate obtained in Comparative Example 1 was subjected to various gas permeability measurements in the same manner as in Example 1. As a result, dryHeTR is 120 cc / (m ² · day · atm), wetHeTR is 109 cc / (m ² · day · atm), O ₂ TR is 3.4 cc / (m ² · day · atm), and WVTR is 1. It was 2 g / (m ² · day). The measurement results are shown in Table 1.

(Comparative Example 2)
Using the same resin substrate, vapor deposition layer and overcoat layer forming coating solution as those used in Example 1, an overcoat layer was formed in the same manner as in Example 1, and resin substrate 11 / vapor deposition layer 12 / A laminate of Comparative Example 2 in which the overcoat layer 13 was laminated in this order was produced. In the gas barrier laminate of Comparative Example 1, the film thickness of each layer was resin base material 11: 12 μm / deposition layer 12: 15 nm / overcoat layer 13: 0.3 μm.

  Next, a tensile load was applied to this laminate using a tensile tester so that the elongation was 8%, and after maintaining for 2 minutes, the load was removed, and a crack-like gap was formed in the vapor deposition layer and the overcoat layer. The plastic deformation rate after the generated tensile test was approximately 2 to 3%.

When this laminate was measured for helium gas permeability, it was 6800 cc / (m ² · day · atm) at 40 ° C. and 0% RH, and 40 ° C. and 90% R.H. H. Then, it was 5620 cc / (m ² · day · atm). From this, it was estimated that the gap was a macropore size with a gap size of 50 nm or more without being condensed and filled with water vapor in a high humidity atmosphere. When the surface was observed with a microscope, cracks with a pitch of about 5 to 30 μm and a width of about 0.1 to 0.3 μm were observed.

[Inspection measurement]
The gas barrier laminate obtained in Comparative Example 2 was subjected to various gas permeability measurements in the same manner as in Example 1. As a result, O ₂ TR was 120 cc / (m ² · day · atm), and WVTR was 45 g / (m ² · day). The measurement results are shown in Table 1.

Measurement results such as layer configuration (materials used) and helium permeability (HeTR), oxygen permeability (O ₂ TR) and water vapor permeability (WVTR) of the laminates obtained in Examples 1 to 3 and Comparative Examples 1 and ₂ are shown. Table 1 summarizes the results. “AC layer” in Table 1 indicates “anchor coat layer”, and “OC layer” in Table 1 indicates “overcoat layer”.

<Evaluation>
In the laminates of Examples 1 to 3, the helium permeability greatly changed with humidity, the helium gas permeability under high humidity was significantly lower than that in a dry state, and high barrier properties were exhibited. It can be seen that despite the extremely low HeTR and O ₂ TR, the water vapor transmission rate is high and the permeation gas selectivity is high. On the other hand, the humidity dependence of the helium permeability of the laminates of Comparative Examples 1 and 2 is small, and the selective permeability of helium, oxygen, and water vapor is not large.

As described above, the gas permeability control laminate of the present invention can easily control the humidity of gas permeability such as helium, and can maintain a high gas barrier property even under high humidity. However, it was confirmed that the permeability of helium and oxygen was extremely low (specifically, O ₂ TR was less than 1 cc / (m ² · day · atm), and WVTR was 10 g / (m ² · day) or more. ). For this reason, it was confirmed that it can be suitably used even for special packaging material applications.

  The gas permeability control laminate of the present invention is easy to control the gas permeability by humidity, has a high level of transparency and durability, and has an excellent gas barrier property such as helium. . It can be widely used in fields that require a transmittance control laminate in a harsh high-humidity atmosphere. For example, it is expected to be suitably used in fields such as (1) packaging films for pharmaceuticals and foods, and (2) prevention of cross leaks in fuel cells, but this is not restrictive.

  In addition, such a gas control laminate can be configured to allow any gas other than water vapor to permeate or shut off, for example, by adjusting the humidity atmosphere arbitrarily, or from the transmittance of so-called switch elements and gases other than water vapor. It is also expected as a sensor element that can predict and measure the humidity.

DESCRIPTION OF SYMBOLS 10 Gas barrier laminated body 11 Resin base material 12 Deposition layer 13 Overcoat layer 14 Slit-like gap 20 Gas barrier laminated body 24 Anchor coat layer 30 Gas barrier laminated body 31 Adhesive layer 32 Laminate resin layer 33 Adhesive layer 34 Laminate resin layer

Claims (10)

  A gas transmission rate comprising a resin substrate and a vapor deposition layer laminated on at least one side of the resin substrate, wherein the vapor deposition layer has a slit-like gap having a width of 2 to 50 nm. Control laminate. An overcoat layer is further provided on the vapor deposition layer,
2. The gas permeability control laminate according to claim 1, wherein the slit-like gap having a width of 2 to 50 nm is provided over the vapor deposition layer or both the vapor deposition layer and the overcoat layer.   The gas permeability control laminate according to claim 1 or 2, wherein a pitch of the slit-shaped gap is 0.1 µm to 10 mm.   Measurement conditions of the laminate: 40 ° C., 0% R.D. H. Helium permeability dryHeTR and measurement conditions of 40 ° C., 90% R.V. H. The gas permeability control laminate according to any one of claims 1 to 3, wherein a ratio d / w to a helium permeability wetHeTR at 5 is 5 or more. The gas permeability control laminate according to any one of claims 1 to 4, further comprising an anchor coat layer between the resin base material and the vapor deposition layer.   The gas permeability control laminate according to any one of claims 1 to 5, wherein a laminate resin layer is further laminated on the overcoat layer via an adhesive layer. A method for producing a gas permeability control laminate,
Forming a laminate in which a vapor deposition layer is laminated on at least one side of the resin base;
Forming a slit-like gap having a width of 2 to 50 nm in the vapor deposition layer by applying a tensile load in at least one direction to the laminate to generate a crack, and a method for producing a gas permeability control laminate. A step of further laminating an overcoat layer on the vapor deposition layer,
The method for producing a gas permeability control laminate according to claim 7, wherein in the step of forming the slit-like gap, the slit-like gap is formed across both the vapor deposition layer and the overcoat layer. .   The method for producing a gas permeability control laminate according to claim 7 or 8, further comprising a step of forming an anchor coat layer between the resin base material and the vapor deposition layer.   The method for producing a gas permeability control laminate according to any one of claims 7 to 9, further comprising a step of laminating a laminate resin layer on the overcoat layer via an adhesive layer.

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