JP2017209802A - Gas barrier laminate and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate capable of exerting excellent gas barrier properties for a long period of time even under a harsh environment, and a manufacturing method thereof.SOLUTION: A gas barrier laminate includes: a resin substrate; a vapor-deposited layer laminated at least on one side of the resin substrate; and an overcoat layer laminated on the vapor-deposited layer. A water vapor permeation degree is 0.5 g/(mday) or less at a measurement condition of 40°C and 90% R.H. A helium transmissivity is 100 cc/(mday atm) or less at a measurement condition of 40°C and 0% R.H.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier laminate and a method for producing the same.

  The gas barrier laminate is a laminate having a property (gas barrier property) that prevents gas such as oxygen and water vapor from permeating. For this reason, the member hold | maintained at the site | part shielded with the gas-barrier laminated body can suppress degradation / deterioration etc. resulting from external gas. In recent years, such gas barrier laminates have been used in various fields.

  Such a gas barrier laminate is used as a packaging material used for packaging foods, for example. In packaging applications such as food, it is required to prevent the contents from being altered. Specifically, it is required to suppress oxidation and alteration of proteins, oils and fats, and to maintain flavor and freshness. For this reason, a gas barrier laminate is preferably used.

  Moreover, such a gas barrier laminate is used as a packaging material used for packaging pharmaceutical products, for example. In packaging applications such as pharmaceuticals, it is required to prevent the contents from being altered. Specifically, it is required to maintain the sterility, suppress the alteration of the active ingredient in the contents, and maintain its efficacy. For this reason, a gas barrier laminate is preferably used.

  Moreover, such a gas barrier laminate is utilized as a packaging material used for packaging electronic parts such as semiconductor wafers and precision parts, for example. When precision parts are exposed to an external gas, the external gas may act as a foreign substance and become a defective product. Therefore, it is required to shield the external gas. For this reason, a gas barrier laminate is preferably used.

  Such a gas barrier laminate is used as a member for flat panel displays such as liquid crystal displays and organic EL displays. In flat panel display applications, it is required to prevent deterioration of internal members such as pixel elements. For this reason, a gas barrier laminate is preferably used.

  Such a gas barrier laminate is used as, for example, a back sheet or a front sheet in a solar cell. In solar cell applications, it is required to prevent deterioration of the internal mechanism from ultraviolet rays and moisture. For this reason, a gas barrier laminate is preferably used.

  When such a gas barrier 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, the presence or absence of damage, the contents The presence or absence of alteration can be ascertained before opening.

  As described above, the gas barrier laminate has not only gas barrier properties but also properties such as transparency, moisture resistance, weather resistance, and durability at a high level so that it can be used for various applications. It is required to be.

  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 in which metal aluminum is evaporated and reacted with 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.

Japanese Patent Laid-Open No. 7-164591 International Publication No. 2004/048081

  However, with the expansion of applications, gas barrier laminates are required to be used in more severe environments. For this reason, further improvements in durability such as moisture resistance, heat resistance, water resistance, and weather resistance are required. Here, as usage modes in a harsh environment, for example, (1) In packaging material applications, processing such as boiling and retort sterilization is performed while being surrounded by packaging materials, (2) In solar cell applications And long-term outdoor use.

  Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a gas barrier laminate that exhibits excellent gas barrier properties over a long period of time even in a harsh environment, and a method for manufacturing the same. To do.

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

The gas barrier laminate according to the present invention includes a resin base material, a vapor deposition layer laminated on at least one side of the resin base material, and an overcoat layer laminated on the vapor deposition layer, and a measurement condition of 40 ° C. 90% R.V. H. Water vapor permeability is 0.5 g / (m ² · day) or less, and the measurement conditions are 40 ° C. and 0% R.D. H. In which the helium permeability is 100 cc / (m ² · day · atm) or less.

  Moreover, the activation energy of helium permeation may be 0.8 to 1.5 times the activation energy of the resin base material.

  Further, the activation energy of water vapor transmission may be twice or more than the activation energy of the resin base material.

  Further, an anchor coat layer may be further provided between the resin base material and the vapor deposition layer.

  Further, at least one or more of a vapor deposition layer and an overcoat layer may be further laminated on the upper layer of the overcoat layer.

  Further, a laminate resin layer may be further laminated on the overcoat layer via an adhesive layer.

  Moreover, an aluminum oxide may be sufficient as a vapor deposition layer, and it is preferable that O / Al ratio is 1.4-2.0 in this case.

  Moreover, the method for producing a gas barrier laminate according to the present invention includes a step of forming an anchor coat layer by applying an anchor coat agent on a resin substrate, and the anchor coat agent has two OH groups. The acrylic polyol having the above and an isocyanate compound having at least two NCO groups in the molecule, the OH group value of the acrylic polyol is 50 mgKOH / g or more and 250 mgKOH / g or less, with respect to the OH group of the acrylic polyol The NCO group equivalent ratio (NCO / OH) of the isocyanate compound is 0.3 or more and 2.5 or less.

  The gas barrier laminate of the present invention suppresses deterioration of the overcoat layer and the vapor deposition layer even under a harsh environment, and exhibits excellent gas barrier properties over a long period of time. Therefore, according to the present invention, gas barrier properties that exhibit excellent gas barrier properties over a long period of time even in severe applications such as boil sterilization and retort sterilization, and in harsh environments such as outdoor placement. A laminate can be provided.

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

  Hereinafter, an embodiment of a gas barrier 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 barrier laminate of this embodiment has a measurement condition of 40 ° C. and 90% R.D. H. The water vapor permeability is 0.5 g / (m ² · day) or less, and the measurement conditions are 40 ° C. and 0% R.D. H. Helium permeability in the water is 100 cc / (m ² · day · atm) or less. This gas barrier laminate can be made into a laminate excellent in durability and the like by limiting the path structure through which helium can pass while having high water vapor barrier properties.

  In particular, in the permeation of helium, the activation energy of permeation is the same as that of the base material (for example, 0.8 to 1.5 times the activation energy of the base material), and the activation energy of water vapor transmission is further increased. By setting the activation energy to 2 or more times, the barrier property and the barrier durability can be improved.

  The activation energy of helium permeation is almost the same as that of the base material. It is considered that the helium permeation is mainly transmitted through the defective part of the barrier layer. Yes, when helium permeates the stack, it is thought that it is mainly passing through a transmission path several times larger than helium molecules. Therefore, if the path structure through which helium can easily pass is reduced, it is considered that water vapor diffuses through a path through which helium cannot permeate, and as a result, the activation energy of water vapor increases.

  By controlling the path structure through which helium permeates, it is possible to suppress locations corresponding to large defects, and to prevent local permeation, so that aging degradation can be remarkably improved. Further, local deterioration in organic EL and solar cells can be achieved. It can also be expected to suppress the occurrence of defects due to transparent transmission, so-called dark spots.

In this embodiment, the transmission activation energy is measured in accordance with JIS K7126 in a temperature range of 30 ° C. or more and 60 ° C. or less, and based on the Arrhenius plot based on the temperature dependence of the transmittance based on Equation (1). Asked.
P = P ₀ × e ^ (− E / RT) (Formula 1)
(P: transmittance, P ₀ : constant, E: activation energy, R: gas constant, T: absolute temperature)

(Gas barrier laminate)
FIG. 1 shows a schematic cross-sectional view of an embodiment of the gas barrier laminate 10 of the present invention. The gas barrier laminate 10 is a laminate having a configuration in which a vapor deposition layer 12 and an overcoat layer 13 are sequentially laminated on one surface of a resin base material 11. 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 barrier 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 barrier laminate 10 of the present embodiment, the thickness of the resin base material 11 is not limited to the above range.

  Further, the resin base material 11 may be subjected to a surface treatment on the surface of the resin base material 11. By performing the surface treatment, adhesion with other layers can be improved in stacking other layers (evaporated 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 in which a reaction is performed while introducing oxygen using a vapor deposition material containing metallic aluminum. 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. More preferably, it is contained at a ratio of 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 in the film formation chamber be 2 × 10 ⁻¹ Pa or less when the gas is introduced. 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 manifested in a gas barrier laminate 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 the silicon compound (A) having a siloxane bond, a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic containing a hydroxyl group and a carboxyl group. It is preferably composed of a component containing any one (B) of polyol, and the inorganic component content ratio in the overcoat layer is 55 wt% or more and 90 wt% or less in terms of SiO ₂ .

  Any one of a coating agent containing a silicon compound (A) having a siloxane bond and a water-soluble polymer having a hydroxyl group, a water-soluble polymer having a carboxyl group, or an acrylic polyol containing a hydroxyl group and a carboxyl group The coating liquid containing (B) 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. If it is 150 degreeC or less, if it is a vapor deposition short time, it will be suitable, without a deformation | transformation of a base material and a crack generating in a vapor deposition film.

  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 barrier 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. The number of defects in the vapor deposition layer can be reduced by the base effect of the vapor deposition layer, the helium permeability is reduced, and it is suitable for barrier properties against oxygen and water vapor.

  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 barrier 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>
In addition, the gas barrier laminate 20 may have a multilayer structure in which at least one pair 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 transmittance of neon and carbon dioxide is high, and the overcoat layer 13 maintains long-term durability.

<Laminated resin layer>
Further, the gas barrier laminate 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-barrier laminated body 30 provided with the laminate resin layer 32 on both surfaces is shown. The gas barrier laminate 30 has an anchor coat layer 24, a vapor deposition layer 12, an overcoat layer 13, an adhesive layer 31, and a laminate resin layer 32 sequentially laminated on one surface of the resin base material 11. This is a laminate in which an adhesive layer 33 and a laminate resin layer 34 are sequentially laminated on the 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, the gas barrier laminate can be sealed with a liquid crystal display element, a transparent conductive sheet used in a solar cell, an electromagnetic wave shield, a touch panel, or the like. It can also be used as a stop 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.

  Hereinafter, examples of the gas barrier laminate of the present invention will be described in detail. However, the gas barrier 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 gas permeability was measured using a differential pressure type gas permeability measuring device GTR-30XT manufactured by Yanaco, measuring the permeability of various gases from 30 to 60 ° C. with a differential pressure of 150 kPa and He as a test gas. The activation energy was obtained from the plot. In addition, the water vapor transmission rate was measured by using a gas adjusted to have a relative humidity of 90% and a total differential pressure of 1 atm. When determining the activation energy, the water vapor partial pressure at each temperature was taken into account. transmittance of _P ^{(H 2 O) g / (} m 2 · day · atm) was calculated based on.

Example 1
First, the vapor deposition layer 12 was formed on the resin base material 11. As the resin base material 11, a 25 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, Inc., T60) having a corona treatment on one surface was used. Further, using a vacuum vapor deposition machine, metal aluminum is evaporated while directly introducing oxygen into the corona-treated surface of the resin base material 11 so that the element ratio O / Al is 1.7. A vapor deposition layer 12 was formed on the material. 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. 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.

  From the above, the gas barrier 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: 15 nm / overcoat layer 13: 0.3 μm.

[Inspection measurement]
The gas barrier laminate of Example 1 was measured for helium gas permeability and found to be 85 cc / (m ² · day · atm). Moreover, the water vapor transmission rate (WVTR) was measured twice: (1) immediately after production (initial stage) and (2) after an accelerated deterioration test (storage test for 500 hours at 60 ° C. and 90% RH). As a result, the initial WVTR was 0.15 g / (m ² · day), and the WVTR after the accelerated deterioration test was 0.21 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 25 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, Inc., T60) having a corona treatment on one surface 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 the 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. The coating solution was a 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate hydrolysis solution (0.001N hydrochloric acid was added as a water and a 6-fold molar equivalent of silylisocyanurate), Tetraethoxysilane was mixed so that silyl isocyanurate: tetraethoxysilane = 20: 80 (molar ratio) and diluted with IPA to obtain 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.

  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, the transmittance measurement of helium gas was 20 cc / (m ² · day · atm), the initial WVTR was 0.07 g / (m ² · day), and the WVTR after the accelerated deterioration test was 0.11 g / (m ² -Day). The measurement results are shown in Table 1.

(Example 3)
The coating solution for overcoat layer formation has the following coating solution composition, and using a vacuum vapor deposition machine as in Example 1, while introducing oxygen so that the element ratio O / Al is 1.5. The metal aluminum was evaporated to form a vapor deposition layer 12 on the resin base material. At this time, the formed vapor deposition layer (AlOx vapor deposition film) was 25 nm in thickness.

  Next, in the same manner as in Example 2, a coating solution for forming an overcoat layer was prepared, the 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.

  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: 25 nm / overcoat layer 13: 0.5 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, the transmittance measurement of the helium gas is ^{11cc / (m 2 · day ·} atm), the initial WVTR is ^{0.05g / (m 2 · day)} , WVTR after accelerated degradation test was 0.09 g / ^{(m 2} -Day). The measurement results are shown in Table 1.

(Comparative Example 1)
As in Example 2, except that a 25 μm thick biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, Inc., T60) having a 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: 25 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, the permeability measurement of helium gas is 120 cc / (m ² · day · atm), the initial WVTR is 1.5 g / (m ² · day), and the WVTR of the accelerated deterioration test is 13 g / (m ² · day). Met. The measurement results are shown in Table 1.

(Comparative Example 2)
For the resin base material 11, a 25 μm-thick biaxially stretched polyethylene terephthalate (PET) film (Toray Industries, Inc., T60) whose one side is corona-treated is used, and a vacuum vapor deposition machine is used. The vapor deposition layer 12 was formed on the resin base material while directly introducing oxygen into the corona-treated surface so that the element ratio O / Si was 1.9. At this time, the formed vapor deposition layer (SiOx vapor deposition film) was 50 nm in thickness.

  The same overcoat layer forming coating solution as that used in Example 1 was used, an overcoat layer was formed in the same manner as in Example 1, and resin base material 11 / deposition layer 12 / overcoat layer 13 were in this order. A gas barrier laminate of Comparative Example 2 laminated with was manufactured. In the gas barrier laminate of Comparative Example 1, the film thickness of each layer was resin base material 11: 25 μm / deposition layer 12: 15 nm / overcoat layer 13: 0.3 μm.

[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, the transmittance measurement of helium gas is 750 cc / (m ² · day · atm), the initial WVTR is 0.4 g / (m ² · day), and the WVTR after the accelerated deterioration test is 2.8 g / ( m ² · day). The measurement results are shown in Table 1.

  Table 1 summarizes the measurement results of layer structures (materials used), helium permeability (HeTR), water vapor permeability (WVTR), etc. of the laminates obtained in Examples 1 to 3 and Comparative Examples 1 and 2. “AC layer” in Table 1 indicates “anchor coat layer”, and “OC layer” in Table 1 indicates “overcoat layer”.

<Evaluation>
As for the gas barrier properties of the gas barrier laminates of Examples 1 to 3, the initial value of WVTR was low, and the gas barrier properties were excellent. Further, even after the accelerated deterioration test, the value of WVTR did not increase so much from the initial value. On the other hand, the gas barrier properties of the gas barrier laminates of Comparative Examples 1 and 2 show that, after the accelerated deterioration test, the value of WVTR is increased by 5 times or more compared to the initial value, and the WVTR is 1.0 g / (m ² · day). ) Larger value.

As described above, the gas barrier laminate of the present invention maintains gas barrier properties even after an accelerated deterioration test (storage test at 60 ° C. and 90% RH for 500 hours) (specifically, WVTR). Was 0.5 g / (m ² · day) or less), and it was confirmed that gas barrier and BR> gata A properties were maintained even in a harsh environment. For this reason, it has been confirmed that it can be suitably used even in harsh environments such as packaging material applications that perform treatments such as boil and retort sterilization, and solar cell applications that are expected to be used for a long time outdoors. It was.

  Since the gas barrier laminate of the present invention has a high level of gas barrier properties, transparency, and durability, it can be widely used in fields requiring a gas barrier laminate. For example, (1) packaging films for pharmaceuticals and foods, (2) packaging films for electronic parts and precision parts such as semiconductor wafers, (3) flat panel display members such as liquid crystal displays and organic EL displays, (4) Although it is expected to be suitably used in fields such as a back sheet application and a front sheet application in a solar cell, it is not limited to this.

DESCRIPTION OF SYMBOLS 10 Gas barrier laminated body 11 Resin base material 12 Deposition layer 13 Overcoat layer 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 (8)

A gas barrier laminate comprising a resin base material, a vapor deposition layer laminated on at least one side of the resin base material, and an overcoat layer laminated on the vapor deposition layer,
Measurement conditions: 40 ° C., 90% R.D. H. The water vapor transmission rate at 0.5 g / (m ² · day) or less,
Measurement conditions: 40 ° C., 0% R.D. H. A gas barrier laminate having a helium permeability of 100 cc / (m ² · day · atm) or less.   The gas barrier laminate according to claim 1, wherein the activation energy of helium permeation is 0.8 to 1.5 times the activation energy of the resin base material.   The gas barrier laminate according to claim 1 or 2, wherein the activation energy of water vapor transmission is at least twice the activation energy of the resin substrate.   The gas barrier laminate according to any one of claims 1 to 3, further comprising an anchor coat layer between the resin base material and the vapor deposition layer.   The gas barrier laminate according to any one of claims 1 to 4, wherein at least one pair of vapor deposition layer and overcoat layer is further laminated on the overcoat layer.   The gas barrier 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.   The gas barrier laminate according to any one of claims 1 to 6, wherein the vapor deposition layer is aluminum oxide and has an O / Al ratio of 1.4 to 2.0. A method for producing a gas barrier laminate according to claim 4,
Including the step of forming the anchor coat layer by applying an anchor coat agent on the resin substrate;
The anchor coating agent contains an acrylic polyol having two or more OH groups and an isocyanate compound having at least two NCO groups in the molecule,
The OH group value of the acrylic polyol is 50 mgKOH / g or more and 250 mgKOH / g or less,
The manufacturing method of the gas-barrier laminated body whose equivalent ratio (NCO / OH) of the NCO group of the said isocyanate compound with respect to OH group of the said acrylic polyol is 0.3-2.5.